Sample records for carlo c-h bond

  1. The Breathing Orbital Valence Bond Method in Diffusion Monte Carlo: C-H Bond Dissociation ofAcetylene

    Energy Technology Data Exchange (ETDEWEB)

    Domin, D.; Braida, Benoit; Lester Jr., William A.


    This study explores the use of breathing orbital valence bond (BOVB) trial wave functions for diffusion Monte Carlo (DMC). The approach is applied to the computation of the carbon-hydrogen (C-H) bond dissociation energy (BDE) of acetylene. DMC with BOVB trial wave functions yields a C-H BDE of 132.4 {+-} 0.9 kcal/mol, which is in excellent accord with the recommended experimental value of 132.8 {+-} 0.7 kcal/mol. These values are to be compared with DMC results obtained with single determinant trial wave functions, using Hartree-Fock orbitals (137.5 {+-} 0.5 kcal/mol) and local spin density (LDA) Kohn-Sham orbitals (135.6 {+-} 0.5 kcal/mol).

  2. C-H fluorination: U can fluorinate unactivated bonds (United States)

    Neumann, Constanze N.; Ritter, Tobias


    Introducing C-F bonds into organic molecules is a challenging task, particularly through C-H activation methods. Now, a uranium-based photocatalyst turns traditional selectivity rules on their heads and fluorinates unfunctionalized alkane Csp3-H bonds, even in the presence of C-H bonds that are typically more reactive.

  3. Catalytic C-H bond silylation of aromatic heterocycles. (United States)

    Toutov, Anton A; Liu, Wen-Bo; Betz, Kerry N; Stoltz, Brian M; Grubbs, Robert H


    This protocol describes a method for the direct silylation of the carbon-hydrogen (C-H) bond of aromatic heterocycles using inexpensive and abundant potassium tert-butoxide (KOt-Bu) as the catalyst. This catalytic cross-dehydrogenative coupling of simple hydrosilanes and various electron-rich aromatic heterocycles enables the synthesis of valuable silylated heteroarenes. The products thus obtained can be used as versatile intermediates, which facilitate the divergent synthesis of pharmaceutically relevant compound libraries from a single Si-containing building block. Moreover, a variety of complex Si-containing motifs, such as those produced by this protocol, are being actively investigated as next-generation therapeutic agents, because they can have improved pharmacokinetic properties compared with the original all-carbon drug molecules. Current competing methods for C-H bond silylation tend to be incompatible with functionalities, such as Lewis-basic heterocycles, that are often found in pharmaceutical substances; this leaves de novo synthesis as the principal strategy for preparation of the target sila-drug analog. Moreover, competing methods tend to be limited in the scope of hydrosilane that can be used, which restricts the breadth of silicon-containing small molecules that can be accessed. The approach outlined in this protocol enables the chemoselective and regioselective late-stage silylation of small heterocycles, including drugs and drug derivatives, with a broad array of hydrosilanes in the absence of precious metal catalysts, stoichiometric reagents, sacrificial hydrogen acceptors or high temperatures. Moreover, H2 is the only by-product generated. The procedure normally requires 48-75 h to be completed.

  4. Metal-Free Oxidative C-C Bond Formation through C-H Bond Functionalization. (United States)

    Narayan, Rishikesh; Matcha, Kiran; Antonchick, Andrey P


    The formation of C-C bonds embodies the core of organic chemistry because of its fundamental application in generation of molecular diversity and complexity. C-C bond-forming reactions are well-known challenges. To achieve this goal through direct functionalization of C-H bonds in both of the coupling partners represents the state-of-the-art in organic synthesis. Oxidative C-C bond formation obviates the need for prefunctionalization of both substrates. This Minireview is dedicated to the field of C-C bond-forming reactions through direct C-H bond functionalization under completely metal-free oxidative conditions. Selected important developments in this area have been summarized with representative examples and discussions on their reaction mechanisms. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Homolytic Bond Dissociation Enthalpies of C C and C-H Bonds in Highly Crowded Alkanes

    Institute of Scientific and Technical Information of China (English)

    ZHU Chen; RUI Lei; FU Yao


    The homolytic C-C and C--H bond dissociation enthalpyies (BDE) of highly crowded alkanes were calcu- lated by using an ONIOM-G3B3 method. Geometric parameters such as bond length, bond angle and molecular volume were carefully investigated, as most of the acyclic alkanes in this study were not yet synthesized. These pa-rameters reflect the influence of steric effect on BDE. Good correlations were found between the rapid decrease of BDE and the increase of molecular volumes. The correlations can be applied to the prediction of the possible exis-tence of many highly strained compounds.

  6. Transition-Metal-Catalyzed Redox-Neutral and Redox-Green C-H Bond Functionalization. (United States)

    Wang, Hongli; Huang, Hanmin


    Transition-metal-catalyzed C-H bond functionalization has become one of the most promising strategies to prepare complex molecules from simple precursors. However, the utilization of environmentally unfriendly oxidants in the oxidative C-H bond functionalization reactions reduces their potential applications in organic synthesis. This account describes our recent efforts in the development of a redox-neutral C-H bond functionalization strategy for direct addition of inert C-H bonds to unsaturated double bonds and a redox-green C-H bond functionalization strategy for realization of oxidative C-H functionalization with O2 as the sole oxidant, aiming to circumvent the problems posed by utilizing environmentally unfriendly oxidants. In principle, these redox-neutral and redox-green strategies pave the way for establishing new environmentally benign transition-metal-catalyzed C-H bond functionalization strategies. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Facile P-C/C-H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes. (United States)

    Zhang, Shaoguang; Li, Haixia; Appel, Aaron M; Hall, Michael B; Bullock, R Morris


    Unusual cleavage of P-C and C-H bonds of the P2 N2 ligand, in heteroleptic [Ni(P2 N2 )(diphosphine)](2+) complexes under mild conditions, results in the formation of an iminium formyl nickelate featuring a C,P,P-tridentate coordination mode. The structures of both the heteroleptic [Ni(P2 N2 )(diphosphine)](2+) complexes and the resulting iminium formyl nickelate have been characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Density functional theory (DFT) calculations were employed to investigate the mechanism of the P-C/C-H bond cleavage, which involves C-H bond cleavage, hydride rotation, Ni-C/P-H bond formation, and P-C bond cleavage.

  8. Transition-Metal-Catalyzed C-H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds. (United States)

    Hummel, Joshua R; Boerth, Jeffrey A; Ellman, Jonathan A


    The transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom-substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functional group compatibility and without the production of waste byproducts. Additionally, many transition-metal-catalyzed C-H bond additions to polarized π bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds.

  9. Amide-directed photoredox-catalysed C-C bond formation at unactivated sp3 C-H bonds (United States)

    Chu, John C. K.; Rovis, Tomislav


    Carbon-carbon (C-C) bond formation is paramount in the synthesis of biologically relevant molecules, modern synthetic materials and commodity chemicals such as fuels and lubricants. Traditionally, the presence of a functional group is required at the site of C-C bond formation. Strategies that allow C-C bond formation at inert carbon-hydrogen (C-H) bonds enable access to molecules that would otherwise be inaccessible and the development of more efficient syntheses of complex molecules. Here we report a method for the formation of C-C bonds by directed cleavage of traditionally non-reactive C-H bonds and their subsequent coupling with readily available alkenes. Our methodology allows for amide-directed selective C-C bond formation at unactivated sp3 C-H bonds in molecules that contain many such bonds that are seemingly indistinguishable. Selectivity arises through a relayed photoredox-catalysed oxidation of a nitrogen-hydrogen bond. We anticipate that our findings will serve as a starting point for functionalization at inert C-H bonds through a strategy involving hydrogen-atom transfer.

  10. Atomic-Scale Kinetic Monte Carlo Simulation of {100}-Oriented Diamond Film Growth in C-H and C-H-Cl Systems by Chemical Vapour Deposition

    Institute of Scientific and Technical Information of China (English)

    安希忠; 张禹; 刘国权; 秦湘阁; 王辅忠; 刘胜新


    We simulate the { 100}-oriented diamond film growth of chemical vapour deposition (CVD) under different modelsin C-H and C-H-CI systems in an atomic scale by using the revised kinetic Monte Carlo method. The sirnulationresults show that: (1) the CVD diamond flm growth in the C-H system is suitable for high substrate temperature,and the flm surface roughness is very coarse; (2) the CVD diamond film can grow in the C-H-C1 system eitherat high temperature or at low temperature, and the film quality is outstanding; (3) atomic CI takes ala activerole for the growth of diamond film, especially at low temperatures. The concentration of atomic C1 should becontrolled in a proper range.

  11. C-H bond activation of methane in aqueous solution: a hybrid quantum mechanical/effective fragment potential study. (United States)

    Da Silva, Júlio C S; Rocha, Willian R


    In this study, we investigated the C-H bond activation of methane catalyzed by the complex [PtCl(4)](2-), using the hybrid quantum mechanical/effective fragment potential (EFP) approach. We analyzed the structures, energetic properties, and reaction mechanism involved in the elementary steps that compose the catalytic cycle of the Shilov reaction. Our B3LYP/SBKJC/cc-pVDZ/EFP results show that the methane activation may proceed through two pathways: (i) electrophilic addition or (ii) direct oxidative addition of the C-H bond of the alkane. The electrophilic addition pathway proceeds in two steps with formation of a σ-methane complex, with a Gibbs free energy barrier of 24.6 kcal mol(-1), followed by the cleavage of the C-H bond, with an energy barrier of 4.3 kcal mol(-1) . The activation Gibbs free energy, calculated for the methane uptake step was 24.6 kcal mol(-1), which is in good agreement with experimental value of 23.1 kcal mol(-1) obtained for a related system. The results shows that the activation of the C-H bond promoted by the [PtCl(4)](2-) catalyst in aqueous solution occurs through a direct oxidative addition of the C-H bond, in a single step, with an activation free energy of 25.2 kcal mol(-1), as the electrophilic addition pathway leads to the formation of a σ-methane intermediate that rapidly undergoes decomposition. The inclusion of long-range solvent effects with polarizable continuum model does not change the activation energies computed at the B3LYP/SBKJC/cc-pVDZ/EFP level of theory significantly, indicating that the large EFP water cluster used, obtained from Monte Carlo simulations and analysis of the center-of-mass radial pair distribution function, captures the most important solvent effects.

  12. Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds. (United States)

    Tian, Hua; Yang, Haijun; Zhu, Changjin; Fu, Hua


    Cross-dehydrogenative couplings of two different C-H bonds have emerged as an attractive goal in organic synthesis. However, achieving regioselective C-H activation is a great challenge because C-H bonds are ubiquitous in organic compounds. Actually, the regioselective couplings promoted by enzymes are a common occurrence in nature. Herein, we have developed simple, efficient and general transition metal-free intramolecular couplings of alphatic and aromatic C-H bonds. The protocol uses readily available aryl triazene as the radical initiator, cheap K2S2O8 as the oxidant, and the couplings were performed well with excellent tolerance of functional groups. Interestingly, α-carbon configuration of some amino acid residues in the substrates was kept after the reactions, and the couplings for substrates with substituted phenylalanine residues exhibited complete β-carbon diastereoselectivity for induction of the chiral α-carbon. Therefore, the present study should provide a novel strategy for regioselective cross-dehydrogenative couplings of two different C-H bonds.

  13. C-H and N-H bond dissociation energies of small aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Barckholtz, C.; Barckholtz, T.A.; Hadad, C.M.


    A survey of computational methods was undertaken to calculate the homolytic bond dissociation energies (BDEs) of the C-H and N-H bonds in monocyclic aromatic molecules that are representative of the functionalities present in coal. These include six-membered rings (benzene, pyridine, pyridazine, pyrimidine, pyrazine) and five-membered rings (furan, thiophene, pyrrole, oxazole). By comparison of the calculated C-H BDEs with the available experimental values for these aromatic molecules, the B3LYP/6-31G(d) level of theory was selected to calculate the BDEs of polycyclic aromatic hydrocarbons (PAHs), including carbonaceous PAHs (naphthalene, anthracene, pyrene, coronene) and heteroatomic PAHs (benzofuran, benzothiophene, indole, benzoxazole, quinoline, isoquinoline, dibenzofuran, carbazole). The cleavage of a C-H or a N-H bond generates a {sigma} radical that is, in general, localized at the site from which the hydrogen atom was removed. However, delocalization of the unpaired electron results in {approximately} 7 kcal {center{underscore}dot} mol{sup {minus}1} stabilization of the radical with respect to the formation of phenyl when the C-H bond is adjacent to a nitrogen atom in the azabenzenes. Radicals from five-membered rings are {approximately} 6 kcal {center{underscore}dot} mol{sup {minus}1} less stable than those formed from six-membered rings due to both localization of the spin density and geometric factors. The location of the heteroatoms in the aromatic ring affects the C-H bond strengths more significantly than does the size of the aromatic network. Therefore, in general, the monocyclic aromatic molecules can be used to predict the C-H BDE of the large PAHs within 1 kcal {center{underscore}dot} mol{sup {minus}1}.

  14. Site-selective and stereoselective functionalization of unactivated C-H bonds (United States)

    Liao, Kuangbiao; Negretti, Solymar; Musaev, Djamaladdin G.; Bacsa, John; Davies, Huw M. L.


    The laboratory synthesis of complex organic molecules relies heavily on the introduction and manipulation of functional groups, such as carbon-oxygen or carbon-halogen bonds; carbon-hydrogen bonds are far less reactive and harder to functionalize selectively. The idea of C-H functionalization, in which C-H bonds are modified at will instead of the functional groups, represents a paradigm shift in the standard logic of organic synthesis. For this approach to be generally useful, effective strategies for site-selective C-H functionalization need to be developed. The most practical solutions to the site-selectivity problem rely on either intramolecular reactions or the use of directing groups within the substrate. A challenging, but potentially more flexible approach, would be to use catalyst control to determine which site in a particular substrate would be functionalized. Here we describe the use of dirhodium catalysts to achieve highly site-selective, diastereoselective and enantioselective C-H functionalization of n-alkanes and terminally substituted n-alkyl compounds. The reactions proceed in high yield, and functional groups such as halides, silanes and esters are compatible with this chemistry. These studies demonstrate that high site selectivity is possible in C-H functionalization reactions without the need for a directing or anchoring group present in the molecule.

  15. Aliphatic C-H---Anion Hydrogen Bonds: Weak Contacts or Strong Interactions?

    Energy Technology Data Exchange (ETDEWEB)

    Hay, Benjamin [ORNL; Pedzisa, Lee [ORNL


    Electronic structure calculations, MP2/aug-cc-pVDZ, are used to determine C H---Cl hydrogen bond energies for a series of XCH3 donor groups in which the electron-withdrawing ability of X is varied over a wide range of values. When attached to polarizing substituents, aliphatic CH groups are moderate to strong hydrogen bond donors, exhibiting interaction energies comparable to those obtained with O H and N H groups. The results explain why aliphatic C H donors are observed to function as competitive binding sites in solution and suggest that such C H---anion contacts should be considered as possible contributors when evaluating the denticity of an anion receptor.

  16. Direct 2-acetoxylation of quinoline N-oxides via copper catalyzed C-H bond activation. (United States)

    Chen, Xuan; Zhu, Chongwei; Cui, Xiuling; Wu, Yangjie


    An efficient and direct 2-acetoxylation of quinoline N-oxides via copper(I) catalyzed C-H bond activation has been developed. This transformation was achieved using TBHP as an oxidant in the cross-dehydrogenative coupling (CDC) reaction of quinoline N-oxides with aldehydes, and provided a practical pathway to 2-acyloxyl quinolines.

  17. Facile P-C/C-H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shaoguang [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Li, Haixia [Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry; Appel, Aaron M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Hall, Michael B. [Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry; Bullock, R. Morris [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)


    Unusual cleavage of P-C and C-H bonds of the P2N2 ligand in heteroleptic [Ni(P2N2)(diphosphine)]2+ complexes results in the formation of an iminium formyl nickelate featuring a C,P,P-tridentate coordination mode.

  18. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan


    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

  19. C-H bond activation by metal-superoxo species: what drives high reactivity? (United States)

    Ansari, Azaj; Jayapal, Prabha; Rajaraman, Gopalan


    Metal-superoxo species are ubiquitous in metalloenzymes and bioinorganic chemistry and are known for their high reactivity and their ability to activate inert C-H bonds. The comparative oxidative abilities of M-O2(.-) species (M = Cr(III), Mn(III), Fe(III), and Cu(II)) towards C-H bond activation reaction are presented. These superoxo species generated by oxygen activation are found to be aggressive oxidants compared to their high-valent metal-oxo counterparts generated by O⋅⋅⋅O bond cleavage. Our calculations illustrate the superior oxidative abilities of Fe(III)- and Mn(III)-superoxo species compared to the others and suggest that the reactivity may be correlated to the magnetic exchange parameter.

  20. Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer (United States)

    Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.


    Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

  1. Time resolved infrared studies of C-H bond activation by organometallics

    Energy Technology Data Exchange (ETDEWEB)

    Asplund, M.C. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley National Lab., CA (United States). Chemical Sciences Div.


    This work describes how step-scan Fourier Transform Infrared spectroscopy and visible and near infrared ultrafast lasers have been applied to the study of the photochemical activation of C-H bonds in organometallic systems, which allow for the selective breaking of C-H bonds in alkanes. The author has established the photochemical mechanism of C-H activation by Tp{sup *}Rh(CO){sub 2}(Tp{sup *} = HB-Pz{sup *}{sub 3}, Pz = 3,5-dimethylpyrazolyl) in alkane solution. The initially formed monocarbonyl forms a weak solvent complex, which undergoes a change in Tp{sup *} ligand connectivity. The final C-H bond breaking step occurs at different time scales depending on the structure of the alkane. In linear solvents, the time scale is <50 ns and cyclic alkanes is {approximately}200 ps. The reactivity of the Tp{sup *}Rh(CO){sub 2} system has also been studied in aromatic solvents. Here the reaction proceeds through two different pathways, with very different time scales. The first proceeds in a manner analogous to alkanes and takes <50 ns. The second proceeds through a Rh-C-C complex, and takes place on a time scale of 1.8 {micro}s.

  2. Rh(III)-Catalyzed C-H Bond Addition/Amine-Mediated Cyclization of Bis-Michael Acceptors. (United States)

    Potter, Tyler J; Ellman, Jonathan A


    A Rh(III)-catalyzed C-H bond addition/primary amine-promoted cyclization of bis-Michael acceptors is reported. The C-H bond addition step occurs with high chemoselectivity, and the subsequent intramolecular Michael addition, mediated by a primary amine catalyst, sets three contiguous stereocenters with high diastereoselectivity. A broad range of directing groups and both aromatic and alkenyl C-H bonds were shown to be effective in this transformation, affording functionalized piperidines, tetrahydropyrans, and cyclohexanes.

  3. Catalytic intermolecular amination of C-H bonds: method development and mechanistic insights. (United States)

    Fiori, Kristin Williams; Du Bois, J


    Reaction methodology for intermolecular C-H amination of benzylic and 3 degrees C-H bonds is described. This process uses the starting alkane as the limiting reagent, gives optically pure tetrasubstituted amines through stereospecific insertion into enantiomeric 3 degrees centers, displays high chemoselectivity for benzylic oxidation, and enables the facile preparation of isotopically enriched 15N-labeled compounds. Access to substituted amines, amino alcohols, and diamines is thereby made possible in a single transformation. Important information relevant to understanding the initial steps in the catalytic cycle, reaction chemoselectivity, the nature of the active oxidant, and pathways for catalyst inactivation has been gained through mechanistic analysis; these studies are also presented.

  4. Mechanism of catalytic functionalization of primary C-H bonds using a silylation strategy. (United States)

    Parija, Abhishek; Sunoj, Raghavan B


    The mechanism of Ir-catalyzed γ-functionalization of a primary sp(3)(C-H) bond in 2-methyl cyclohexanol is examined using the density functional theory (M06). The nature of the active catalyst for the initial silylation of alcohol is identified as the monomer derived from [Ir(cod)OMe]2 while that for γ-sp(3)(C-H) activation leading to oxasilolane is [IrH(nbe)(phen)]. The rate-determining step is found to involve Si-C coupling through reductive elimination.

  5. Chelation-assisted palladium-catalyzed direct cyanation of 2-arylpyridine C-H bonds. (United States)

    Jia, Xiaofei; Yang, Dongpeng; Zhang, Shouhui; Cheng, Jiang


    A chelation-assisted palladium-catalyzed ortho-cyanation of the sp2 C-H bond by CuCN provided aromatic nitriles in moderate to good yields. Notably, the reaction could be conducted on a 10 mmol scale. The key intermediate of the natural product of Menispermum dauricum DC was concisely synthesized by the procedure. This new approach represents an exceedingly practical method for the synthesis of aromatic nitriles and offers an attractive alternative to the traditional Sandmeyer reaction.

  6. The synthesis of functionalized bridged polycycles via C-H bond insertion. (United States)

    Shih, Jiun-Le; Chen, Po-An; May, Jeremy A


    This review presents examples from the chemical literature of syntheses of bridged-polycyclic products via C-H bond insertion by carbenes and nitrenes. Applications to natural product synthesis, a description of the essential elements in substrate-controlled reactions, and mechanistic details of transformations are presented. Overall, these transformations allow the construction of important ring systems rapidly and efficiently, though additional catalyst development is needed.

  7. Theoretical study of the C-H bond dissociation energy of acetylene (United States)

    Taylor, Peter R.; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.


    The authors present a theoretical study of the convergence of the C-H bond dissociation energy (D sub o) of acetylene with respect to both the one- and n-particle spaces. Their best estimate for D sub o of 130.1 plus or minus 1.0 kcal/mole is slightly below previous theoretical estimates, but substantially above the value determined using Stark anticrossing spectroscopy that is asserted to be an upper bound.

  8. Asymmetric Intramolecular Alkylation of Chiral Aromatic Imines via Catalytic C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Watzke, Anja; Wilson, Rebecca; O' Malley, Steven; Bergman, Robert; Ellman, Jonathan


    The asymmetric intramolecular alkylation of chiral aromatic aldimines, in which differentially substituted alkenes are tethered meta to the imine, was investigated. High enantioselectivities were obtained for imines prepared from aminoindane derivatives, which function as directing groups for the rhodium-catalyzed C-H bond activation. Initial demonstration of catalytic asymmetric intramolecular alkylation also was achieved by employing a sterically hindered achiral imine substrate and catalytic amounts of a chiral amine.

  9. Origins of Protons in C-H Bond Insertion Products of Phenols: Proton-Self-Sufficient Function via Water Molecules. (United States)

    Luo, Zhoujie; Gao, Ya; Zhu, Tong; Zhang, John Zenghui; Xia, Fei


    Water molecules can serve as proton shuttles for proton transfer in the C-H bond insertion reactions catalyzed by transition metal complexes. Recently, the control experiments performed for C-H bond insertion of phenol and anisol by gold carbenes show that large discrepancy exists in the yields of hydrogenated and deuterated products. Thus, we conducted a detailed theoretical analysis on the function of water molecules in the C-H bond insertion reactions. The comparison of calculated results and control experiments indicates that the solution water molecules play a crucial role of proton shuttle in C-H bond insertion. In particular, it was found that the hydroxyl groups in phenols were capable of donating protons via water shuttles for the production of C-H products, which had a substantial influence on the yields of inserted products. The hydroxyl groups instead of C-H bonds in phenols function like "proton reservoirs" in the C-H bond insertion, which we call the "proton self-sufficient" (PSS) function of phenol. The PSS function of phenol indicates that the substrates with and without proton reservoirs will lead to different C-H bond insertion products.

  10. Inserting CO2 into Aryl C-H Bonds of Metal-Organic Frameworks: CO2 Utilization for Direct Heterogeneous C-H Activation. (United States)

    Gao, Wen-Yang; Wu, Haifan; Leng, Kunyue; Sun, Yinyong; Ma, Shengqian


    Described for the first time is that carbon dioxide (CO2 ) can be successfully inserted into aryl C-H bonds of the backbone of a metal-organic framework (MOF) to generate free carboxylate groups, which serve as Brønsted acid sites for efficiently catalyzing the methanolysis of epoxides. The work delineates the very first example of utilizing CO2 for heterogeneous C-H activation and carboxylation reactions on MOFs, and opens a new avenue for CO2 chemical transformations under mild reaction conditions.

  11. Modification of Purine and Pyrimidine Nucleosides by Direct C-H Bond Activation

    Directory of Open Access Journals (Sweden)

    Yong Liang


    Full Text Available Transition metal-catalyzed modifications of the activated heterocyclic bases of nucleosides as well as DNA or RNA fragments employing traditional cross-coupling methods have been well-established in nucleic acid chemistry. This review covers advances in the area of cross-coupling reactions in which nucleosides are functionalized via direct activation of the C8-H bond in purine and the C5-H or C6-H bond in uracil bases. The review focuses on Pd/Cu-catalyzed couplings between unactivated nucleoside bases with aryl halides. It also discusses cross-dehydrogenative arylations and alkenylations as well as other reactions used for modification of nucleoside bases that avoid the use of organometallic precursors and involve direct C-H bond activation in at least one substrate. The scope and efficiency of these coupling reactions along with some mechanistic considerations are discussed.

  12. Reactivity of mononuclear alkylperoxo copper(II) complex. O-O bond cleavage and C-H bond activation. (United States)

    Kunishita, Atsushi; Ishimaru, Hirohito; Nakashima, Satoru; Ogura, Takashi; Itoh, Shinobu


    A detailed reactivity study has been carried out for the first time on a new mononuclear alkylperoxo copper(II) complex, which is generated by the reaction of copper(II) complex supported by the bis(pyridylmethyl)amine tridentate ligand containing a phenyl group at the 6-position of the pyridine donor groups and cumene hydroperoxide (CmOOH) in CH3CN. The cumylperoxo copper(II) complex thus obtained has been found to undergo homolytic cleavage of the O-O bond and induce C-H bond activation of exogenous substrates, providing important insights into the catalytic mechanism of copper monooxygenases.

  13. Selective molecular recognition, C-H bond activation, and catalysis in nanoscale reaction vessels

    Energy Technology Data Exchange (ETDEWEB)

    Fiedler, Dorothea; Leung, Dennis H.; Raymond, Kenneth N.; Bergman, Robert G.


    Supramolecular chemistry represents a way to mimic enzyme reactivity by using specially designed container molecules. We have shown that a chiral self-assembled M{sub 4}L{sub 6} supramolecular tetrahedron can encapsulate a variety of cationic guests, with varying degrees of stereoselectivity. Reactive iridium guests can be encapsulated and the C-H bond activation of aldehydes occurs, with the host cavity controlling the ability of substrates to interact with the metal center based upon size and shape. In addition, the host container can act as a catalyst by itself. By restricting reaction space and preorganizing the substrates into reactive conformations, it accelerates the sigmatropic rearrangement of enammonium cations.

  14. Rhodium(III)-catalyzed indazole synthesis by C-H bond functionalization and cyclative capture. (United States)

    Lian, Yajing; Bergman, Robert G; Lavis, Luke D; Ellman, Jonathan A


    An efficient, one-step, and highly functional group-compatible synthesis of substituted N-aryl-2H-indazoles is reported via the rhodium(III)-catalyzed C-H bond addition of azobenzenes to aldehydes. The regioselective coupling of unsymmetrical azobenzenes was further demonstrated and led to the development of a new removable aryl group that allows for the preparation of indazoles without N-substitution. The 2-aryl-2H-indazole products also represent a new class of readily prepared fluorophores for which initial spectroscopic characterization has been performed.

  15. Regioselective borylation of the C-H bonds in alkylamines and alkyl ethers. Observation and origin of high reactivity of primary C-H bonds beta to nitrogen and oxygen. (United States)

    Li, Qian; Liskey, Carl W; Hartwig, John F


    Borylation of aliphatic C-H bonds in alkylamines and alkyl ethers to form primary aminoalkyl and alkoxyalkyl boronate esters and studies on the origin of the regioselectivity of these reactions are reported. The products of these reactions can be used directly in Suzuki-Miyaura cross-coupling reactions or isolated as air-stable potassium trifluoroborate salts. Selective borylation of the terminal C-H bond at the positions β to oxygen and nitrogen occurs in preference to borylation of the other terminal C-H bonds. Experimental studies and computational results show that C-H bond cleavage is the rate-determining step of the current borylation reactions. The observed higher reactivity of C-H bonds at the terminal position of ethylamines and ethers results from a combination of attractive Lewis acid-base and hydrogen-bonding interactions, as well as typical repulsive steric interactions, in the transition state. In this transition state, the heteroatom lies directly above the boron atom of one boryl ligand, creating a stabilizing interaction between the weak Lewis acid and Lewis base, and a series of C-H bonds of the substrate lie near the oxygen atoms of the boryl ligands, participating in a set of weak C-H···O interactions that lead to significant stabilization of the transition state forming the major product.

  16. Insertion of singlet chlorocarbenes across C-H bonds in alkanes: Evidence for two phase mechanism

    Indian Academy of Sciences (India)

    M Ramalingam; K Ramasami; P Venuvanalingam


    Transition states for the insertion reactions of singlet mono and dichlorocarbenes (1CHCl and 1CCl2) into C-H bonds of alkanes (methane, ethane, propane and -butane) have been investigated at MP2 and DFT levels with 6-31g ( , ) basis set. The of 1CHCl and 1CCl2 may interact with alkane’s filled fragment orbital of either or symmetry. So chlorocarbenes insertion reactions have been investigated for both (/) approaches. The approach has been adjudicated to be the minimum energy path over the approach both at the MP2 and DFT levels. Mulliken, NPA and ESP derived charge analyses have been carried out along the minimal energy reaction path using the IRC method for 1CHCl and 1CCl2 insertions into the primary and secondary C-H bonds of propane. The occurrence of TSs either in the electrophilic or nucleophilic phase has been identified through NBO charge analyses in addition to the net charge flow from alkane to the carbene moiety.

  17. Silylation of C-H bonds in aromatic heterocycles by an Earth-abundant metal catalyst (United States)

    Toutov, Anton A.; Liu, Wen-Bo; Betz, Kerry N.; Fedorov, Alexey; Stoltz, Brian M.; Grubbs, Robert H.


    Heteroaromatic compounds containing carbon-silicon (C-Si) bonds are of great interest in the fields of organic electronics and photonics, drug discovery, nuclear medicine and complex molecule synthesis, because these compounds have very useful physicochemical properties. Many of the methods now used to construct heteroaromatic C-Si bonds involve stoichiometric reactions between heteroaryl organometallic species and silicon electrophiles or direct, transition-metal-catalysed intermolecular carbon-hydrogen (C-H) silylation using rhodium or iridium complexes in the presence of excess hydrogen acceptors. Both approaches are useful, but their limitations include functional group incompatibility, narrow scope of application, high cost and low availability of the catalysts, and unproven scalability. For this reason, a new and general catalytic approach to heteroaromatic C-Si bond construction that avoids such limitations is highly desirable. Here we report an example of cross-dehydrogenative heteroaromatic C-H functionalization catalysed by an Earth-abundant alkali metal species. We found that readily available and inexpensive potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, furnishing heteroarylsilanes in a single step. The silylation proceeds under mild conditions, in the absence of hydrogen acceptors, ligands or additives, and is scalable to greater than 100 grams under optionally solvent-free conditions. Substrate classes that are difficult to activate with precious metal catalysts are silylated in good yield and with excellent regioselectivity. The derived heteroarylsilane products readily engage in versatile transformations enabling new synthetic strategies for heteroaromatic elaboration, and are useful in their own right in pharmaceutical and materials science applications.

  18. Fine Control over Site and Substrate Selectivity in Hydrogen Atom Transfer-Based Functionalization of Aliphatic C-H Bonds. (United States)

    Salamone, Michela; Carboni, Giulia; Bietti, Massimo


    The selective functionalization of unactivated aliphatic C-H bonds over intrinsically more reactive ones represents an ongoing challenge of synthetic chemistry. Here we show that in hydrogen atom transfer (HAT) from the aliphatic C-H bonds of alkane, ether, alcohol, amide, and amine substrates to the cumyloxyl radical (CumO(•)) fine control over site and substrate selectivity is achieved by means of acid-base interactions. Protonation of the amines and metal ion binding to amines and amides strongly deactivates the C-H bonds of these substrates toward HAT to CumO(•), providing a powerful method for selective functionalization of unactivated or intrinsically less reactive C-H bonds. With 5-amino-1-pentanol, site-selectivity has been drastically changed through protonation of the strongly activating NH2 group, with HAT that shifts to the C-H bonds that are adjacent to the OH group. In the intermolecular selectivity studies, trifluoroacetic acid, Mg(ClO4)2, and LiClO4 have been employed in a orthogonal fashion for selective functionalization of alkane, ether, alcohol, and amide (or amine) substrates in the presence of an amine (or amide) one. Ca(ClO4)2, that promotes deactivation of amines and amides by Ca(2+) binding, offers, moreover, the opportunity to selectively functionalize the C-H bonds of alkane, ether, and alcohol substrates in the presence of both amines and amides.

  19. Are non-linear C-H⋯O contacts hydrogen bonds or Van der Waals interactions?. Establishing the limits between hydrogen bonds and Van der Waals interactions (United States)

    Novoa, Juan J.; Lafuente, Pilar; Mota, Fernando


    The hydrogen bond nature of angular C-H⋯O contacts is examined to determine when these contacts are better classified as hydrogen bonds or as Van der Waals bonds. To classify the bond we propose to look at the nature of the intermolecular bond critical point present in the electron density of the complex containing the bond. The physics behind this approach is explained using a qualitative orbital overlap model aimed at describing the main changes in the electronic density of the complex produced by the C-H⋯O bending.

  20. Oxygenation via C-H/C-C Bond Activation with Molecular Oxygen. (United States)

    Liang, Yu-Feng; Jiao, Ning


    The selective oxidation of organic molecules is a fundamentally important component of modern synthetic chemistry. In the past decades, direct oxidative C-H and C-C bond functionalization has proved to be one of the most efficient and straightforward methods to synthesize complex products from simple and readily available starting materials. Among these oxidative processes, the use of molecular oxygen as a green and sustainable oxidant has attracted considerable attention because of its highly atom-economical, abundant, and environmentally friendly characteristics. The development of new protocols using molecular oxygen as an ideal oxidant is highly desirable in oxidation chemistry. More importantly, the oxygenation reaction of simple molecules using molecular oxygen as the oxygen source offers one of the most ideal processes for the construction of O-containing compounds. Aerobic oxidation and oxygenation by enzymes, such as monooxygenase, tyrosinase, and dopamine β-monooxygenase, have been observed in some biological C-H bond hydroxylation processes. Encouraged by these biological transformations, transition-metal- or organocatalyst-catalyzed oxygenation through dioxygen activation has attracted academic and industrial prospects. In this Account, we describe some advances from our group in oxygenation via C-H/C-C bond activation with molecular oxygen as the oxidant and oxygen source for the synthesis of O-containing compounds. Under an atmosphere of O2 (1 atm) or air (1 atm), we have successfully incorporated one or two O atoms from O2 into simple and readily available substrates through C-H, C-C, C═C, and C≡C bond cleavage by transition-metal catalysis, organocatalysis, and photocatalysis. Moreover, we have devised cyclization reactions with molecular oxygen to construct O-heterocycles. Most of these transformations can tolerate a broad range of functional groups. Furthermore, on the basis of isotope labeling experiments, electron paramagnetic resonance

  1. N-heterocyclic carbene gold(I) and copper(I) complexes in C-H bond activation. (United States)

    Gaillard, Sylvain; Cazin, Catherine S J; Nolan, Steven P


    Environmental concerns have and will continue to have a significant role in determining how chemistry is carried out. Chemists will be challenged to develop new, efficient synthetic processes that have the fewest possible steps leading to a target molecule, the goal being to decrease the amount of waste generated and reduce energy use. Along this path, chemists will need to develop highly selective reactions with atom-economical pathways producing nontoxic byproduct. In this context, C-H bond activation and functionalization is an extremely attractive method. Indeed, for most organic transformations, the presence of a reactive functionality is required. In Total Synthesis, the "protection and deprotection" approach with such reactive groups limits the overall yield of the synthesis, involves the generation of significant chemical waste, costs energy, and in the end is not as green as one would hope. In turn, if a C-H bond functionalization were possible, instead of the use of a prefunctionalized version of the said C-H bond, the number of steps in a synthesis would obviously be reduced. In this case, the C-H bond can be viewed as a dormant functional group that can be activated when necessary during the synthetic strategy. One issue increasing the challenge of such a desired reaction is selectivity. The cleavage of a C-H bond (bond dissociation requires between 85 and 105 kcal/mol) necessitates a high-energy species, which could quickly become a drawback for the control of chemo-, regio-, and stereoselectivity. Transition metal catalysts are useful reagents for surmounting this problem; they can decrease the kinetic barrier of the reaction yet retain control over selectivity. Transition metal complexes also offer important versatility in having distinct pathways that can lead to activation of the C-H bond. An oxidative addition of the metal in the C-H bond, and a base-assisted metal-carbon bond formation in which the base can be coordinated (or not) to the metal

  2. Dimethylphosphinate bridged binuclear Rh(i) catalysts for the alkoxycarbonylation of aromatic C-H bonds. (United States)

    Iturmendi, Amaia; Sanz Miguel, Pablo J; Popoola, Saheed A; Al-Saadi, Abdulaziz A; Iglesias, Manuel; Oro, Luis A


    A variety of binuclear rhodium(i) complexes featuring two bridging dimethylphosphinate ligands ((CH3)2PO2(-)) have been prepared and tested in the alkoxycarbonylation of aromatic C-H bonds. The complex [Rh(μ-κO,O'-(CH3)2PO2)(cod)]2 has been prepared by a reaction of [Rh(μ-MeO)(cod)]2 with 2 equivalents of dimethylphosphinic acid. Binuclear complexes [Rh(μ-κO,O'-(CH3)2PO2)(CO)L]2 (L = PPh3, P(OMe)Ph2 and P(OPh)3) were obtained by carbonylation of the related mononuclear complexes [Rh(κO-(CH3)2PO2)(cod)(L)], which were prepared in situ by the reaction of [Rh(μ-κO,O'-(CH3)2PO2)(cod)]2 with 2 equivalents of L. Conversely, if L = IPr, the reaction of [Rh(μ-κO,O'-(CH3)2PO2)(CO)L]2 with carbon monoxide affords the mononuclear complex [Rh(κO-(CH3)2PO2)(CO)2IPr]. The subsequent reaction with trimethylamine N-oxide gives the corresponding binuclear complex [Rh(μ-κO,O'-(CH3)2PO2)(CO)(IPr)]2 by abstraction of one of the carbonyl ligands. Complexes [Rh(μ-κO,O'-(CH3)2PO2)(cod)]2 and [Rh(κO-(CH3)2PO2)(cod)(L)] (L = IPr, PPh3, P(OMe)Ph2, P(OPh)3) are active precatalysts in the alkoxycarbonylation of C-H bonds, with the ligand system playing a key role in the catalytic activity. The complexes that feature more labile Rh-L bonds give rise to better catalysts, probably due to the more straightforward substitution of L by a second carbonyl ligand, since a more electrophilic carbonyl carbon atom is more susceptible toward aryl migration. In fact, complexes [Rh(μ-κO,O'-(CH3)2PO2)(CO)2]2 and [Rh(μ-Cl)(CO)2]2, generated in situ from [Rh(μ-κO,O'-(CH3)2PO2)(cod)]2 and [Rh(μ-Cl)(cod)2]2, respectively, are the most active catalysts tested in this work.

  3. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan


    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  4. Direct functionalization of nitrogen heterocycles via Rh-catalyzed C-H bond activation. (United States)

    Lewis, Jared C; Bergman, Robert G; Ellman, Jonathan A


    [Reaction: see text]. Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct functionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes our work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. We initially discovered an intramolecular Rh-catalyzed C-2 alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. We then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, we discovered that a novel substrate-derived Rh- N-heterocyclic carbene (NHC) complex was involved as an intermediate. We then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy 3)2] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazoline, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy 3) 2 fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid cocatalysts accelerate the alkylation, we developed conditions that efficiently and intermolecularly alkylate a variety of

  5. At least 10% shorter C-H bonds in cryogenic protein crystal structures than in current AMBER forcefields. (United States)

    Pang, Yuan-Ping


    High resolution protein crystal structures resolved with X-ray diffraction data at cryogenic temperature are commonly used as experimental data to refine forcefields and evaluate protein folding simulations. However, it has been unclear hitherto whether the C-H bond lengths in cryogenic protein structures are significantly different from those defined in forcefields to affect protein folding simulations. This article reports the finding that the C-H bonds in high resolution cryogenic protein structures are 10-14% shorter than those defined in current AMBER forcefields, according to 3709 C-H bonds in the cryogenic protein structures with resolutions of 0.62-0.79 Å. Also, 20 all-atom, isothermal-isobaric, 0.5-μs molecular dynamics simulations showed that chignolin folded from a fully-extended backbone formation to the native β-hairpin conformation in the simulations using AMBER forcefield FF12SB at 300 K with an aggregated native state population including standard error of 10 ± 4%. However, the aggregated native state population with standard error reduced to 3 ± 2% in the same simulations except that C-H bonds were shortened by 10-14%. Furthermore, the aggregated native state populations with standard errors increased to 35 ± 3% and 26 ± 3% when using FF12MC, which is based on AMBER forcefield FF99, with and without the shortened C-H bonds, respectively. These results show that the 10-14% bond length differences can significantly affect protein folding simulations and suggest that re-parameterization of C-H bonds according to the cryogenic structures could improve the ability of a forcefield to fold proteins in molecular dynamics simulations. Copyright © 2015 The Author. Published by Elsevier Inc. All rights reserved.

  6. Consequences of metal-oxide interconversion for C-H bond activation during CH4 reactions on Pd catalysts. (United States)

    Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique


    Mechanistic assessments based on kinetic and isotopic methods combined with density functional theory are used to probe the diverse pathways by which C-H bonds in CH4 react on bare Pd clusters, Pd cluster surfaces saturated with chemisorbed oxygen (O*), and PdO clusters. C-H activation routes change from oxidative addition to H-abstraction and then to σ-bond metathesis with increasing O-content, as active sites evolve from metal atom pairs (*-*) to oxygen atom (O*-O*) pairs and ultimately to Pd cation-lattice oxygen pairs (Pd(2+)-O(2-)) in PdO. The charges in the CH3 and H moieties along the reaction coordinate depend on the accessibility and chemical state of the Pd and O centers involved. Homolytic C-H dissociation prevails on bare (*-*) and O*-covered surfaces (O*-O*), while C-H bonds cleave heterolytically on Pd(2+)-O(2-) pairs at PdO surfaces. On bare surfaces, C-H bonds cleave via oxidative addition, involving Pd atom insertion into the C-H bond with electron backdonation from Pd to C-H antibonding states and the formation of tight three-center (H3C···Pd···H)(‡) transition states. On O*-saturated Pd surfaces, C-H bonds cleave homolytically on O*-O* pairs to form radical-like CH3 species and nearly formed O-H bonds at a transition state (O*···CH3(•)···*OH)(‡) that is looser and higher in enthalpy than on bare Pd surfaces. On PdO surfaces, site pairs consisting of exposed Pd(2+) and vicinal O(2-), Pd(ox)-O(ox), cleave C-H bonds heterolytically via σ-bond metathesis, with Pd(2+) adding to the C-H bond, while O(2-) abstracts the H-atom to form a four-center (H3C(δ-)···Pd(ox)···H(δ+)···O(ox))(‡) transition state without detectable Pd(ox) reduction. The latter is much more stable than transition states on *-* and O*-O* pairs and give rise to a large increase in CH4 oxidation turnover rates at oxygen chemical potentials leading to Pd to PdO transitions. These distinct mechanistic pathways for C-H bond activation, inferred from theory

  7. C-H(ax)...Y(ax) contacts in cyclohexane derivatives revisited-identification of improper hydrogen-bonded contacts. (United States)

    Kolocouris, Antonios


    The structure of 111 cyclohexane derivatives bearing the axial substitution Y(ax)-C was optimized at the B3LYP/6-31+G(d,p) level. The natural bond orbital analysis revealed the presence of overlap interactions between the axial substituent and the antibonding sigma*(C-Hax) orbitals; these calculated hyperconjugative interactions suggest the presence of improper H-bonded contacts. The addition of an appropriate bridging fragment between the axial substituent and cyclohexane carbon strengthens significantly the hydrogen-bonding component of the contact and several structures of axially substituted cyclohexane derivatives including such hydrogen-bonded C-H(ax)...Y(ax)-C contacts were retrieved from the Cambridge Crystallographic Database. Overall, the calculations predicted that the C-H(ax)...Y(ax)-C contacts in common cyclohexane derivatives that are generally thought to be steric in nature (Pauli repulsive forces) include an improper hydrogen-bonding component.

  8. Graphene Oxide Catalyzed C-H Bond Activation: The Importance Oxygen Functional Groups for Biaryl Construction

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Yongjun; Tang, Pei; Zhou, Hu; Zhang, Wei; Yang, Hanjun; Yan, Ning; Hu, Gang; Mei, Donghai; Wang, Jianguo; Ma, Ding


    A heterogeneous, inexpensive and environment-friendly carbon catalytic system was developed for the C-H bond arylation of benzene resulting in the subsequent formation of biaryl compounds. The oxygen-containing groups on these graphene oxide sheets play an essential role in the observed catalytic activity. The catalytic results of model compounds and DFT calculations show that these functional groups promote this reaction by stabilization and activation of K ions at the same time of facilitating the leaving of I. And further mechanisms studies show that it is the charge induced capabilities of oxygen groups connected to specific carbon skeleton together with the giant π-reaction platform provided by the π-domain of graphene that played the vital roles in the observed excellent catalytic activity. D. Mei acknowledges the support from the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory.

  9. Asymmetric Synthesis of (-)-Incarvillateine Employing an Intramolecular Alkylation via Rh-Catalyzed Olefinic C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, Andy; Bergman, Robert; Ellman, Jonathan


    An asymmetric total synthesis of (-)-incarvillateine, a natural product having potent analgesic properties, has been achieved in 11 steps and 15.4% overall yield. The key step is a rhodium-catalyzed intramolecular alkylation of an olefinic C-H bond to set two stereocenters. Additionally, this transformation produces an exocyclic, tetrasubstituted alkene through which the bicyclic piperidine moiety can readily be accessed.

  10. Asymmetric Synthesis of (-)-Incarvillateine Employing an Intramolecular Alkylation via Rh-Catalyzed Olefinic C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, Andy; Bergman, Robert; Ellman, Jonathan


    An asymmetric total synthesis of (-)-incarvillateine, a natural product having potent analgesic properties, has been achieved in 11 steps and 15.4% overall yield. The key step is a rhodium-catalyzed intramolecular alkylation of an olefinic C-H bond to set two stereocenters. Additionally, this transformation produces an exocyclic, tetrasubstituted alkene through which the bicyclic piperidine moiety can readily be accessed.

  11. Control of the Chemoselectivity of Metal N-Aryl Nitrene Reactivity: C-H Bond Amination versus Electrocyclization. (United States)

    Kong, Chen; Jana, Navendu; Jones, Crystalann; Driver, Tom G


    A mechanism study to identify the elements that control the chemoselectivity of metal-catalyzed N-atom transfer reactions of styryl azides is presented. Our studies show that the proclivity of the metal N-aryl nitrene to participate in sp(3)-C-H bond amination or electrocyclization reactions can be controlled by either the substrate or the catalyst. Electrocyclization is favored for mono-β-substituted and sterically noncongested styryl azides, whereas sp(3)-C-H bond amination through an H-atom abstraction-radical recombination mechanism is preferred when a tertiary allylic reaction center is present. Even when a weakened allylic C-H bond is present, our data suggest that the indole is still formed through an electrocyclization instead of a common allyl radical intermediate. The site selectivity of metal N-aryl nitrenes was found to be controlled by the choice of catalyst: Ir(I)-alkene complexes trigger electrocyclization processes while Fe(III) porphyrin complexes catalyze sp(3)-C-H bond amination in substrates where Rh2(II) carboxylate catalysts provide both products.

  12. Remote C-H alkylation and C-C bond cleavage enabled by an in situ generated palladacycle (United States)

    Ye, Juntao; Shi, Zhihao; Sperger, Theresa; Yasukawa, Yoshifumi; Kingston, Cian; Schoenebeck, Franziska; Lautens, Mark


    The direct and selective functionalization of C-H bonds of arenes is one of the most challenging yet valuable aims in organic synthesis. Despite notable recent achievements, a pre-installed directing group proved to be essential in most of the methodologies reported so far. In this context, the use of a transient directing group that can be generated in situ has attracted attention and demonstrated the great potential of this strategy. Here we report the use of an in situ generated palladacycle to accomplish remote-selective C-H alkylation reactions of arenes. Following the C-H functionalization event, the alkylated aryl ring undergoes a formal migration to provide diversely substituted benzofuran and indole scaffolds. Computational studies revealed that a palladium(IV) intermediate is not involved in the alkylation step. The aryl migration was found to proceed through a sequential C-C bond cleavage, insertion and β-hydride-elimination process. The increasing steric bulk that builds up during the C-H functionalization step drives the unusual C-C bond cleavage in a non-strained system.

  13. Synthesis of a Benzodiazepine-derived Rhodium NHC Complex by C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Bergman, Roberg G.; Gribble, Jr., Michael W.; Ellman, Jonathan A.


    The synthesis and characterization of a Rh(I)-NHC complex generated by C-H activation of 1,4-benzodiazepine heterocycle are reported. This complex constitutes a rare example of a carbene tautomer of a 1,4-benzodiazepine aldimine stabilized by transition metal coordination and demonstrates the ability of the catalytically relevant RhCl(PCy{sub 3}){sub 2} fragment to induce NHC-forming tautomerization of heterocycles possessing a single carbene-stabilizing heteroatom. Implications for the synthesis of benzodiazepines and related pharmacophores via C-H functionalization are discussed.

  14. Direct approaches to nitriles via highly efficient nitrogenation strategy through C-H or C-C bond cleavage. (United States)

    Wang, Teng; Jiao, Ning


    Because of the importance of nitrogen-containing compounds in chemistry and biology, organic chemists have long focused on the development of novel methodologies for their synthesis. For example, nitrogen-containing compounds show up within functional materials, as top-selling drugs, and as bioactive molecules. To synthesize these compounds in a green and sustainable way, researchers have focused on the direct functionalization of hydrocarbons via C-H or C-C bond cleavage. Although researchers have made significant progress in the direct functionalization of simple hydrocarbons, direct C-N bond formation via C-H or C-C bond cleavage remains challenging, in part because of the unstable character of some N-nucleophiles under oxidative conditions. The nitriles are versatile building blocks and precursors in organic synthesis. Recently, chemists have achieved the direct C-H cyanation with toxic cyanide salts in the presence of stoichiometric metal oxidants. In this Account, we describe recent progress made by our group in nitrile synthesis. C-H or C-C bond cleavage is a key process in our strategy, and azides or DMF serve as the nitrogen source. In these reactions, we successfully realized direct nitrile synthesis using a variety of hydrocarbon groups as nitrile precursors, including methyl, alkenyl, and alkynyl groups. We could carry out C(sp(3))-H functionalization on benzylic, allylic, and propargylic C-H bonds to produce diverse valuable synthetic nitriles. Mild oxidation of C═C double-bonds and C≡C triple-bonds also produced nitriles. The incorporation of nitrogen within the carbon skeleton typically involved the participation of azide reagents. Although some mechanistic details remain unclear, studies of these nitrogenation reactions implicate the involvement of a cation or radical intermediate, and an oxidative rearrangement of azide intermediate produced the nitrile. We also explored environmentally friendly oxidants, such as molecular oxygen, to make our

  15. Aliphatic C-H bond oxidation of toluene using copper peroxo complexes that are stable at room temperature. (United States)

    Würtele, Christian; Sander, Ole; Lutz, Volker; Waitz, Thomas; Tuczek, Felix; Schindler, Siegfried


    Dinuclear copper peroxo complexes obtained from mononuclear copper(I) complexes showed extremely high stabilities under ambient conditions in the solid state and could be heated above 100 degrees C without decomposition. The increased stability could be explained with regard to their molecular structures. Furthermore, the four complexes investigated showed a high potential for aliphatic C-H bond oxidations: for example, technical-grade toluene was oxidized to benzaldehyde in yields of up to 20%.

  16. I2-Mediated 2H-indazole synthesis via halogen-bond-assisted benzyl C-H functionalization. (United States)

    Yi, Xiangli; Jiao, Lei; Xi, Chanjuan


    I2-Mediated benzyl C-H functionalization has been developed for the synthesis of 2H-indazoles, which features high efficiency, simple conditions and no need for metals. Mechanistic experiments and DFT calculations have revealed halogen bond assistance and a radical chain process for this reaction. The azo group and the bound iodine cooperate in the hydrogen abstraction step, which circumvents the thermodynamic disfavor of direct hydrogen abstraction by a simple iodine radical.

  17. Cobalt(III)-catalyzed synthesis of indazoles and furans by C-H bond functionalization/addition/cyclization cascades. (United States)

    Hummel, Joshua R; Ellman, Jonathan A


    The development of operationally straightforward and cost-effective routes for the assembly of heterocycles from simple inputs is important for many scientific endeavors, including pharmaceutical, agrochemical, and materials research. In this article we describe the development of a new air-stable cationic Co(III) catalyst for convergent, one-step benchtop syntheses of N-aryl-2H-indazoles and furans by C-H bond additions to aldehydes followed by in situ cyclization and aromatization. Only a substoichiometric amount of AcOH is required as an additive that is both low-cost and convenient to handle. The syntheses of these heterocycles are the first examples of Co(III)-catalyzed additions to aldehydes, and reactions are demonstrated for a variety of aromatic, heteroaromatic, and aliphatic derivatives. The syntheses of both N-aryl-2H-indazoles and furans have been performed on 20 mmol scales and should be readily applicable to larger scales. The reported heterocycle syntheses also demonstrate the use of directing groups that have not previously been applied to Co(III)-catalyzed C-H bond functionalizations. Additionally, the synthesis of furans demonstrates the first example of Co(III)-catalyzed functionalization of alkenyl C-H bonds.

  18. Palladium(II)-Catalyzed C-H Bond Activation/C-C and C-O Bond Formation Reaction Cascade: Direct Synthesis of Coumestans. (United States)

    Neog, Kashmiri; Borah, Ashwini; Gogoi, Pranjal


    A palladium catalyzed cascade reaction of 4-hydroxycoumarins and in situ generated arynes has been developed for the direct synthesis of coumestans. This cascade strategy proceeds via C-H bond activation/C-O and C-C bond formations in a single reaction vessel. This methodology affords moderate to good yields of coumestans and is tolerant of a variety of functional groups including halide. The methodology was applied to the synthesis of natural product flemichapparin C.

  19. C-H bond strengths and acidities in aromatic systems: effects of nitrogen incorporation in mono-, di-, and triazines. (United States)

    Wren, Scott W; Vogelhuber, Kristen M; Garver, John M; Kato, Shuji; Sheps, Leonid; Bierbaum, Veronica M; Lineberger, W Carl


    The negative ion chemistry of five azine molecules has been investigated using the combined experimental techniques of negative ion photoelectron spectroscopy to obtain electron affinities (EA) and tandem flowing afterglow-selected ion tube (FA-SIFT) mass spectrometry to obtain deprotonation enthalpies (Δ(acid)H(298)). The measured Δ(acid)H(298) for the most acidic site of each azine species is combined with the EA of the corresponding radical in a thermochemical cycle to determine the corresponding C-H bond dissociation energy (BDE). The site-specific C-H BDE values of pyridine, 1,2-diazine, 1,3-diazine, 1,4-diazine, and 1,3,5-triazine are 110.4 ± 2.0, 111.3 ± 0.7, 113.4 ± 0.7, 107.5 ± 0.4, and 107.8 ± 0.7 kcal mol(-1), respectively. The application of complementary experimental methods, along with quantum chemical calculations, to a series of nitrogen-substituted azines sheds light on the influence of nitrogen atom substitution on the strength of C-H bonds in six-membered rings.

  20. C-H bond activation of benzene by unsaturated η2-cyclopropene and η2-benzyne complexes of niobium. (United States)

    Boulho, Cédric; Oulié, Pascal; Vendier, Laure; Etienne, Michel; Pimienta, Véronique; Locati, Abel; Bessac, Fabienne; Maseras, Feliu; Pantazis, Dimitrios A; McGrady, John E


    We report the synthesis of a niobium cyclopropyl complex, Tp(Me2)NbMe(c-C(3)H(5))(MeCCMe), and show that thermal loss of methane from this compound generates an intermediate that is capable of activating both aliphatic and aromatic C-H bonds. Isotopic labeling, trapping studies, a detailed kinetic analysis, and density functional theory all suggest that the active intermediate is an η(2)-cyclopropene complex formed via β-hydrogen abstraction rather than an isomeric cyclopropylidene species. C-H activation chemistry of this type represents a rather unusual reactivity pattern for η(2)-alkene complexes but is favored in this case by the strain in the C(3) ring which prevents the decomposition of the key intermediate via loss of cyclopropene.

  1. Understanding trends in C-H bond activation in heterogeneous catalysis (United States)

    Latimer, Allegra A.; Kulkarni, Ambarish R.; Aljama, Hassan; Montoya, Joseph H.; Yoo, Jong Suk; Tsai, Charlie; Abild-Pedersen, Frank; Studt, Felix; Nørskov, Jens K.


    While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.

  2. Synthesis of a tricyclic mescaline analogue by catalytic C-H bond activation. (United States)

    Ahrendt, Kateri A; Bergman, Robert G; Ellman, Jonathan A


    [reaction: see text] A tetrahydrobis(benzofuran) mescaline analogue has been prepared in six steps and 38% overall yield from (4'-O-methyl)methyl gallate. The key step in this synthesis is a tandem cyclization reaction via directed C[bond]H activation followed by olefin insertion.

  3. Rh-Catalyzed, Regioselective, C-H Bond Functionalization: Access to Quinoline-Branched Amines and Dimers. (United States)

    Reddy, M Damoder; Fronczek, Frank R; Watkins, E Blake


    Rh-catalyzed, chelation-induced, C-5 regioselective C-H functionalization of 8-amidoquinolines with a range of N-Boc aminals is reported for the first time. The addition of in situ generated imines to C(sp(2))-H bonds afforded branched amines in good to excellent yields. Moreover, this transformation features good functional group compatibility, broad substrate scope, and mild reaction conditions and is suitable for gram-scale synthesis. In addition, an unprecedented, chelation-induced, site-selective, remote dimerization of quinolines led to the formation of dimer frameworks in moderate yields under Rh-catalyzed conditions.

  4. Reactivity control of C-H bond activation over vanadium-silver bimetallic oxide cluster cations. (United States)

    Li, Xiao-Na; Wu, Xiao-Nan; Ding, Xun-Lei; Xu, Bo; He, Sheng-Gui


    Vanadium-silver bimetallic oxide cluster ions (V(x)Ag(y)O(z)(+); x=1-4, y=1-4, z=3-11) are produced by laser ablation and reacted with ethane in a fast-flow reactor. A reflectron time of flight (Re-TOF) mass spectrometer is used to detect the cluster distribution before and after the reactions. Hydrogen atom abstraction (HAA) reactions are identified over VAgO(3)(+), V(2)Ag(2)O(6)(+), V(2)Ag(4)O(7)(+), V(3)AgO(8)(+), V(3)Ag(3)O(9)(+), and V(4)Ag(2)O(11)(+) ions, in which the oxygen-centered radicals terminally bonded on V atoms are active sites for the facile HAA reactions. DFT calculations are performed to study the structures, bonding, and reactivity. The reaction mechanisms of V(2)Ag(2)O(6)(+) +C(2)H(6) are also given. The doped Ag atoms with a valence state of +1 are highly dispersed at the periphery of the V(x)Ag(y)O(z)(+) cluster ions. The reactivity can be well-tuned gradually by controlling the number of Ag atoms. The steric protection due to the peripherally bonded Ag atoms greatly enhances the selectivity of the V-Ag bimetallic oxide clusters with respect to the corresponding pure vanadium oxide systems. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Ruthenium(II)-catalyzed synthesis of pyrrole- and indole-fused isocoumarins by C-H bond activation in DMF and water

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Sawant, S.G.; Dixneuf, P.H.

    -C-H bond activation offer efficient routes for a fast access to various functional molecules.[12] Initially palladium catalysts were used for the direct C-H functionalization of heterocycles,[13,14] however tremendous progress has been made..., in terms of synthesis efficiency,atom economy and process cost, with the less expensive ruthenium(0)[15] and especially the more stable, even in water, ruthenium(II)catalysts[16--17]for cross C- C bond formation fromsp2C-H bonds.A wide range of N...

  6. C-H Bond Activation by Early Transition Metal Carbide Cluster Anion MoC3 (-). (United States)

    Li, Zi-Yu; Hu, Lianrui; Liu, Qing-Yu; Ning, Chuan-Gang; Chen, Hui; He, Sheng-Gui; Yao, Jiannian


    Although early transition metal (ETM) carbides can activate CH bonds in condensed-phase systems, the electronic-level mechanism is unclear. Atomic clusters are ideal model systems for understanding the mechanisms of bond activation. For the first time, CH activation of a simple alkane (ethane) by an ETM carbide cluster anion (MoC3 (-) ) under thermal-collision conditions has been identified by using high-resolution mass spectrometry, photoelectron imaging spectroscopy, and high-level quantum chemical calculations. Dehydrogenation and ethene elimination were observed in the reaction of MoC3 (-) with C2 H6 . The CH activation follows a mechanism of oxidative addition that is much more favorable in the carbon-stabilized low-spin ground electronic state than in the high-spin excited state. The reaction efficiency between the MoC3 (-) anion and C2 H6 is low (0.23±0.05) %. A comparison between the anionic and a highly efficient cationic reaction system (Pt(+) +C2 H6 ) was made. It turned out that the potential-energy surfaces for the entrance channels of the anionic and cationic reaction systems can be very different. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts. (United States)

    Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A


    As a society, we are heavily dependent on nonrenewable petroleum-derived fuels and chemical feedstocks. Rapid depletion of these resources and the increasingly evident negative effects of excess atmospheric CO2 drive our efforts to discover ways of converting excess CO2 into energy dense chemical fuels through selective C-H bond formation and using renewable energy sources to supply electrons. In this way, a carbon-neutral fuel economy might be realized. To develop a molecular or heterogeneous catalyst for C-H bond formation with CO2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H(-) to CO2, rather than recombining with H(+) to liberate H2. Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO2. Of particular interest are the nitride- and carbide-containing clusters: [Fe4N(CO)12](-) and its derivatives and [Fe4C(CO)12](2-). In both aqueous and mixed solvent conditions, [Fe4N(CO)12](-) forms a reduced hydride intermediate, [H-Fe4N(CO)12](-), through stepwise electron and proton transfers. This hydride selectively reacts with CO2 and generates formate with >95% efficiency. The mechanism for this transformation is supported by crystallographic, cyclic voltammetry, and spectroelectrochemical (SEC) evidence. Furthermore, installation of a proton shuttle onto [Fe4N(CO)12](-) facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO2; only H2 is observed in this case. In contrast, isoelectronic [Fe4C(CO)12](2-) features a concerted proton-electron transfer mechanism to form [H-Fe4C(CO)12](2-), which is selective for H2 production even in the presence of CO2, in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none promote C-H bond formation. Thermochemical

  8. Copper-Catalyzed Redox-Triggered Remote C-H Functionalization: Highly Selective Formation of C-CF3 and C-O Bonds

    Institute of Scientific and Technical Information of China (English)

    Taotao Li; Peng Yu; Jin-Shun Lin; Yonggang Zhi; Xin-Yuan Liu


    A Cu-catalyzed remote sp3 C-H/unactivated alkenes functionalization reaction for the concomitant construction ofC-CF3 and C-O bonds was described.An 1,5-H radical transfer involving an sp3 C-H bond adjacent to a nitrogen atom and an α-CF3-alkyl radical intermediate derived from unactivated alkenes was observed and demonstrated to proceed via the radical process.

  9. Pyridine N-Oxide vs Pyridine Substrates for Rh(III)-Catalyzed Oxidative C-H Bond Functionalization. (United States)

    Neufeldt, Sharon R; Jiménez-Osés, Gonzalo; Huckins, John R; Thiel, Oliver R; Houk, K N


    The origin of the high reactivity and site selectivity of pyridine N-oxide substrates in O-pivaloyl hydroxamic acid-directed Rh(III)-catalyzed (4+2) annulation reactions with alkynes was investigated computationally. The reactions of the analogous pyridine derivatives were previously reported to be slower and to display poor site selectivity for functionalization of the C(2)-H vs the C(4)-H bonds of the pyridine ring. The N-oxide substrates are found to be more reactive overall because the directing group interacts more strongly with Rh. For N-oxide substrates, alkyne insertion is rate-limiting and selectivity-determining in the reaction with a dialkyl alkyne, but C-H activation can be selectivity-determining with other coupling partners such as terminal alkynes. The rates of reaction with a dialkyl alkyne at the two sites of a pyridine substrate are limited by two different steps: C-H activation is limiting for C(2)-functionalization, while alkyne insertion is limiting for C(4)-functionalization. Consistent with the observed poor site selectivity in the reaction of a pyridine substrate, the overall energy barriers for functionalization of the two positions are nearly identical. High C(2)-selectivity in the C-H activation step of the reaction of the N-oxide is due to a cooperative effect of the C-H Brønsted acidity, the strength of the forming C-Rh bond, and intramolecular electrostatic interactions between the [Rh]Cp* and the heteroaryl moieties. On the other hand, some of these forces are in opposition in the case of the pyridine substrate, and C(4)-H activation is moderately favored overall. The alkyne insertion step is favored at C(2) over C(4) for both substrates, and this preference is largely influenced by electrostatic interactions between the alkyne and the heteroarene. Experimental results that support these calculations, including kinetic isotope effect studies, H/D exchange studies, and results using a substituted pyridine, are also described.

  10. Iron-Carbonyl-Catalyzed Redox-Neutral [4+2] Annulation of N-H Imines and Internal Alkynes by C-H Bond Activation. (United States)

    Jia, Teng; Zhao, Chongyang; He, Ruoyu; Chen, Hui; Wang, Congyang


    Stoichiometric C-H bond activation of arenes mediated by iron carbonyls was reported by Pauson as early as in 1965, yet the catalytic C-H transformations have not been developed. Herein, an iron-catalyzed annulation of N-H imines and internal alkynes to furnish cis-3,4-dihydroisoquinolines is described, and represents the first iron-carbonyl-catalyzed C-H activation reaction of arenes. Remarkablely, this is also the first redox-neutral [4+2] annulation of imines and alkynes proceeding by C-H activation. The reaction also features only cis stereoselectivity and excellent atom economy as neither base, nor external ligand, nor additive is required. Experimental and theoretical studies reveal an oxidative addition mechanism for C-H bond activation to afford a dinuclear ferracycle and a synergetic diiron-promoted H-transfer to the alkyne as the turnover-determining step.

  11. Oxygen activation and intramolecular C-H bond activation by an amidate-bridged diiron(II) complex. (United States)

    Jones, Matthew B; Hardcastle, Kenneth I; Hagen, Karl S; MacBeth, Cora E


    A diiron(II) complex containing two μ-1,3-(κN:κO)-amidate linkages has been synthesized using the 2,2',2''-tris(isobutyrylamido)triphenylamine (H(3)L(iPr)) ligand. The resulting diiron complex, 1, reacts with dioxygen (or iodosylbenzene) to effect intramolecular C-H bond activation at the methine position of the ligand isopropyl group. The ligand-activated product, 2, has been isolated and characterized by a variety of methods including X-ray crystallography. Electrospray ionization mass spectroscopy of 2 prepared from(18)O(2) was used to confirm that the oxygen atom incorporated into the ligand framework is derived from molecular oxygen.

  12. Monte Carlo simulation of AB-copolymers with saturating bonds

    DEFF Research Database (Denmark)

    Chertovich, A.C.; Ivanov, V.A.; Khokhlov, A.R.


    Structural transitions in a single AB-copolymer chain where saturating bonds can be formed between A- and B-units are studied by means of Monte Carlo computer simulations using the bond fluctuation model. Three transitions are found, coil-globule, coil-hairpin and globule-hairpin, depending...... to those of diblock sequences than to the properties of random sequences. The model (although quite rough) is expected to represent some basic features of real RNA molecules, i.e. the formation of secondary structure of RNA due to hydrogen bonding of corresponding bases and stacking interactions...

  13. Rh(III)/Cu(II)-cocatalyzed synthesis of 1H-indazoles through C-H amidation and N-N bond formation. (United States)

    Yu, Da-Gang; Suri, Mamta; Glorius, Frank


    Substituted 1H-indazoles can be formed from readily available arylimidates and organo azides by Rh(III)-catalyzed C-H activation/C-N bond formation and Cu-catalyzed N-N bond formation. For the first time the N-H-imidates are demonstrated to be good directing groups in C-H activation, also capable of undergoing intramolecular N-N bond formation. The process is scalable and green, with O2 as the terminal oxidant and N2 and H2O formed as byproducts. Moreover, the products could be transformed to diverse important derivatives.

  14. Importance of the C-H...N weak hydrogen bonding on the coordination structures of manganese(III) porphyrin complexes. (United States)

    Ikezaki, Akira; Nakamura, Mikio


    The reactions between Mn(Por)Cl and Bu(4)N(+)CN(-) have been examined in various solvents by UV-vis and (1)H NMR spectroscopy, where Por's are dianions of meso-tetraisopropylporphyrin (T(i)PrP), meso-tetraphenylporphyrin (TPP), meso-tetrakis(p-(trifluoromethyl)phenyl)porphyrin (p-CF(3)-TPP), meso-tetramesitylporphyrin (TMP), and meso-tetrakis(2,6-dichlorophenyl)porphyrin (2,6-Cl(2)-TPP). Population ratios of the reaction products, Mn(Por)(CN) and [Mn(Por)(CN)(2)](-), have been sensitively affected by the solvents used. In the case of Mn(T(i)PrP)Cl, the following results are obtained: (i) The bis-adduct is preferentially formed in dipolar aprotic solvents such as DMSO, DMF, and acetonitrile. (ii) Both the mono- and bis-adduct are formed in the less polar solvents such as CH(2)Cl(2) and benzene though the complete conversion to the bis-adduct is achieved with much smaller amount of the ligand in benzene solution. (iii) Only the mono-adduct is formed in CHCl(3) solution even in the presence of a large excess of cyanide. (iv) Neither the mono- nor the bis-adduct is obtained in methanol solution. The results mentioned above have been explained in terms of the C-H.N and O-H.N hydrogen bonding in chloroform and methanol solutions, respectively, between the solvent molecules and cyanide ligand; hydrogen bonding weakens the coordination ability of cyanide and reduces the population of the bis-adduct. The importance of the C-H.N weak hydrogen bonding is most explicitly shown in the following fact: while the starting complex is completely converted to the bis-adduct in CH(2)Cl(2) solution, the conversion from the mono- to the bis-adduct is not observed even in the presence of 7000 equiv of Bu(4)N(+)CN(-) in CHCl(3) solution. The effective magnetic moments of the bis-adduct has been determined by the Evans method to be 3.2 micro(B) at 25 degrees C, suggesting that the complex adopts the usual (d(xy))(2)(d(xz), d(yz))(2) electron configuration despite the highly ruffled

  15. Tuning reactivity and selectivity in hydrogen atom transfer from aliphatic C-H bonds to alkoxyl radicals: role of structural and medium effects. (United States)

    Salamone, Michela; Bietti, Massimo


    Hydrogen atom transfer (HAT) is a fundamental reaction that takes part in a wide variety of chemical and biological processes, with relevant examples that include the action of antioxidants, damage to biomolecules and polymers, and enzymatic and biomimetic reactions. Moreover, great attention is currently devoted to the selective functionalization of unactivated aliphatic C-H bonds, where HAT based procedures have been shown to play an important role. In this Account, we describe the results of our recent studies on the role of structural and medium effects on HAT from aliphatic C-H bonds to the cumyloxyl radical (CumO(•)). Quantitative information on the reactivity and selectivity patterns observed in these reactions has been obtained by time-resolved kinetic studies, providing a deeper understanding of the factors that govern HAT from carbon and leading to the definition of useful guidelines for the activation or deactivation of aliphatic C-H bonds toward HAT. In keeping with the electrophilic character of alkoxyl radicals, polar effects can play an important role in the reactions of CumO(•). Electron-rich C-H bonds are activated whereas those that are α to electron withdrawing groups are deactivated toward HAT, with these effects being able to override the thermodynamic preference for HAT from the weakest C-H bond. Stereoelectronic effects can also influence the reactivity of the C-H bonds of ethers, amines, and amides. HAT is most rapid when these bonds can be eclipsed with a lone pair on an adjacent heteroatom or with the π-system of an amide functionality, thus allowing for optimal orbital overlap. In HAT from cyclohexane derivatives, tertiary axial C-H bond deactivation and tertiary equatorial C-H bond activation have been observed. These effects have been explained on the basis of an increase in torsional strain or a release in 1,3-diaxial strain in the HAT transition states, with kH(eq)/kH(ax) ratios that have been shown to exceed one order of

  16. Manganese-Substituted Myoglobin: Characterization and Reactivity of an Oxidizing Intermediate towards a Weak C-H Bond

    Directory of Open Access Journals (Sweden)

    Kari L. Stone


    Full Text Available Metal-substituted hemoproteins have been examined by biochemists for decades, but their potential for diverse functionalities has not been thoroughly investigated. By replacing hemoproteins with non-native metals, heme-containing proteins could be capable of performing a range of chemistries not allowed for in the native protein. The metal within the heme of the oxygen-carrying hemoprotein, myoglobin, can readily be replaced with other first row transition metals such as cobalt, chromium and manganese. Upon oxidation with two-electron oxidants (ex. meta-chloroperbenzoic acid, an oxidizing intermediate is produced in manganese-substituted myoglobin. Electron paramagnetic resonance analyses confirm the oxidation of Mn(III to Mn(IV. With the addition of weak C-H bonds of 1,4 cyclohexadiene, hydrogen atom abstraction is exhibited by the oxidizing intermediate that displays a second-order rate constant of 2.79 +/− 0.22 M−1 s−1 by the metal-oxo species. The replacement of the iron ion with a manganese ion at the active site of myoglobin displays oxidative capabilities that are not shown in native myoglobin.

  17. Facile fabrication of magnetically recyclable metal-organic framework nanocomposites for highly efficient and selective catalytic oxidation of benzylic C-H bonds. (United States)

    Chen, Yifa; Huang, Xianqiang; Feng, Xiao; Li, Jikun; Huang, Yingyu; Zhao, Jingshu; Guo, Yuexin; Dong, Xinmei; Han, Ruodan; Qi, Pengfei; Han, Yuzhen; Li, Haiwei; Hu, Changwen; Wang, Bo


    HKUST-1@Fe3O4 chemically bonded core-shell nanoparticles have been prepared by growing HKUST-1 thin layers joined by carboxyl groups onto Fe3O4 nanospheres. These magnetic core-shell MOF nanostructures show exceptional catalytic activity for the oxidation of benzylic C-H bonds and they can be recovered by magnetic separation and reused without losing any activity.

  18. Identification of the Chemical Bonding Prompting Adhesion of a-C:H Thin Films on Ferrous Alloy Intermediated by a SiCx:H Buffer Layer. (United States)

    Cemin, F; Bim, L T; Leidens, L M; Morales, M; Baumvol, I J R; Alvarez, F; Figueroa, C A


    Amorphous carbon (a-C) and several related materials (DLCs) may have ultralow friction coefficients that can be used for saving-energy applications. However, poor chemical bonding of a-C/DLC films on metallic alloys is expected, due to the stability of carbon-carbon bonds. Silicon-based intermediate layers are employed to enhance the adherence of a-C:H films on ferrous alloys, although the role of such buffer layers is not yet fully understood in chemical terms. The chemical bonding of a-C:H thin films on ferrous alloy intermediated by a nanometric SiCx:H buffer layer was analyzed by X-ray photoelectron spectroscopy (XPS). The chemical profile was inspected by glow discharge optical emission spectroscopy (GDOES), and the chemical structure was evaluated by Raman and Fourier transform infrared spectroscopy techniques. The nature of adhesion is discussed by analyzing the chemical bonding at the interfaces of the a-C:H/SiCx:H/ferrous alloy sandwich structure. The adhesion phenomenon is ascribed to specifically chemical bonding character at the buffer layer. Whereas carbon-carbon (C-C) and carbon-silicon (C-Si) bonds are formed at the outermost interface, the innermost interface is constituted mainly by silicon-iron (Si-Fe) bonds. The oxygen presence degrades the adhesion up to totally delaminate the a-C:H thin films. The SiCx:H deposition temperature determines the type of chemical bonding and the amount of oxygen contained in the buffer layer.

  19. Palladium-catalyzed meta-selective C-H bond activation with a nitrile-containing template: computational study on mechanism and origins of selectivity. (United States)

    Yang, Yun-Fang; Cheng, Gui-Juan; Liu, Peng; Leow, Dasheng; Sun, Tian-Yu; Chen, Ping; Zhang, Xinhao; Yu, Jin-Quan; Wu, Yun-Dong; Houk, K N


    Density functional theory investigations have elucidated the mechanism and origins of meta-regioselectivity of Pd(II)-catalyzed C-H olefinations of toluene derivatives that employ a nitrile-containing template. The reaction proceeds through four major steps: C-H activation, alkene insertion, β-hydride elimination, and reductive elimination. The C-H activation step, which proceeds via a concerted metalation-deprotonation (CMD) pathway, is found to be the rate- and regioselectivity-determining step. For the crucial C-H activation, four possible active catalytic species-monomeric Pd(OAc)2, dimeric Pd2(OAc)4, heterodimeric PdAg(OAc)3, and trimeric Pd3(OAc)6-have been investigated. The computations indicated that the C-H activation with the nitrile-containing template occurs via a Pd-Ag heterodimeric transition state. The nitrile directing group coordinates with Ag while the Pd is placed adjacent to the meta-C-H bond in the transition state, leading to the observed high meta-selectivity. The Pd2(OAc)4 dimeric mechanism also leads to the meta-C-H activation product but with higher activation energies than the Pd-Ag heterodimeric mechanism. The Pd monomeric and trimeric mechanisms require much higher activation free energies and are predicted to give ortho products. Structural and distortion energy analysis of the transition states revealed significant effects of distortions of the template on mechanism and regioselectivity, which provided hints for further developments of new templates.

  20. AgNO2-mediated direct nitration of the quinoxaline tertiary benzylic C-H bond and direct conversion of 2-methyl quinoxalines into related nitriles. (United States)

    Wu, Degui; Zhang, Jian; Cui, Jianhai; Zhang, Wei; Liu, Yunkui


    A unique method for AgNO2-mediated direct nitration of the quinoxaline tertiary C-H bond and direct conversion of 2-methyl quinoxalines into 2-quinoxaline nitriles under oxidative conditions has been developed. This protocol provides an efficient way to access quinoxaline containing nitroalkanes and nitriles depending on different substrate selection.

  1. Mechanistic insight into conjugated N-N bond cleavage by Rh(III)-catalyzed redox-neutral C-H activation of pyrazolones. (United States)

    Wu, Weirong; Liu, Yuxia; Bi, Siwei


    Density functional theory (DFT) calculations have been performed to investigate the detailed mechanism of Rh(III)-catalyzed redox-neutral C-H activation of pyrazolones with PhC≡CPh. It is found that (1) the methylene C-H activation is prior to the phenyl C-H activation, (2) the N-N bond cleavage is realized via Rh(III) → Rh(I) → Rh(III) rather than via Rh(III) → Rh(V) → Rh(III). The zwitterionic Rh(I) complex is identified to be a key intermediate in promoting the N-N bond cleavage. (3) Different from the Rh(III)-catalyzed hydrazine-directed C-H activation for indole synthesis, the rate-determining step of the reaction studied in this work is the Rh(III) → Rh(I) → Rh(III) process resulting in the N-N bond cleavage rather than the alkyne insertion step. The present theoretical study provides new insight into the mechanism of the conjugated N-N bond cleavage.

  2. Valence-bond quantum Monte Carlo algorithms defined on trees. (United States)

    Deschner, Andreas; Sørensen, Erik S


    We present a class of algorithms for performing valence-bond quantum Monte Carlo of quantum spin models. Valence-bond quantum Monte Carlo is a projective T=0 Monte Carlo method based on sampling of a set of operator strings that can be viewed as forming a treelike structure. The algorithms presented here utilize the notion of a worm that moves up and down this tree and changes the associated operator string. In quite general terms, we derive a set of equations whose solutions correspond to a whole class of algorithms. As specific examples of this class of algorithms, we focus on two cases. The bouncing worm algorithm, for which updates are always accepted by allowing the worm to bounce up and down the tree, and the driven worm algorithm, where a single parameter controls how far up the tree the worm reaches before turning around. The latter algorithm involves only a single bounce where the worm turns from going up the tree to going down. The presence of the control parameter necessitates the introduction of an acceptance probability for the update.

  3. Bond-updating mechanism in cluster Monte Carlo calculations (United States)

    Heringa, J. R.; Blöte, H. W. J.


    We study a cluster Monte Carlo method with an adjustable parameter: the number of energy levels of a demon mediating the exchange of bond energy with the heat bath. The efficiency of the algorithm in the case of the three-dimensional Ising model is studied as a function of the number of such levels. The optimum is found in the limit of an infinite number of levels, where the method reproduces the Wolff or the Swendsen-Wang algorithm. In this limit the size distribution of flipped clusters approximates a power law more closely than that for a finite number of energy levels.

  4. Unprecedented Reaction Pathway of Sterically Crowded Calcium Complexes: Sequential C-N Bond Cleavage Reactions Induced by C-H Bond Activations. (United States)

    Yang, Yang; Wang, Haobing; Ma, Haiyan


    Five bis(quinolylmethyl)-(1H-indolylmethyl)amine (BQIA) compounds, that is, {(quinol-8-yl-CH2 )2 NCH2 (3-Br-1H-indol-2-yl)} (L(1) H) and {[(8-R(3) -quinol-2-yl)CH2 ]2 NCH(R(2) )[3-R(1) -1H-indol-2-yl]} (L(2-5) H) (L(2) H: R(1) =Br, R(2) =H, R(3) =H; L(3) H: R(1) =Br, R(2) =H, R(3) =iPr; L(4) H: R(1) =H, R(2) =CH3 , R(3) =iPr; L(5) H: R(1) =H, R(2) =nBu, R(3) =iPr) were synthesized and used to prepare calcium complexes. The reactions of L(1-5) H with silylamido calcium precursors (Ca[N(SiMe2 R)2 ]2 (THF)2 , R=Me or H) at room temperature gave heteroleptic products (L(1, 2) )CaN(SiMe3 )2 (1, 2), (L(3, 4) )CaN(SiHMe2 )2 (3 a, 4 a) and homoleptic complexes (L(3, 5) )2 Ca (D3, D5). NMR and X-ray analyses proved that these calcium complexes were stabilized through Ca⋅⋅⋅C-Si, Ca⋅⋅⋅H-Si or Ca⋅⋅⋅H-C agostic interactions. Unexpectedly, calcium complexes ((L(3-5) )CaN(SiMe3 )2 ) bearing more sterically encumbered ligands of the same type were extremely unstable and underwent C-N bond cleavage processes as a consequence of intramolecular C-H bond activation, leading to the exclusive formation of (E)-1,2-bis(8-isopropylquinol-2-yl)ethane. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Infrared and Raman spectroscopy and quantum chemistry calculation studies of C H⋯O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoate (United States)

    Sato, Harumi; Dybal, Jiří; Murakami, Rumi; Noda, Isao; Ozaki, Yukihiro


    This review paper reports infrared (IR) and Raman spectroscopy and quantum chemistry calculation studies of C-H⋯O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoates. IR and Raman spectra were measured for poly(3-hydroxybutyrate) (PHB) and a new type of bacterial copolyester, poly(3-hydroxybutyrate- co-3-hydroxyhexanoate), P(HB- co-HHx) (HHx=12 mol%) over a temperature range of 20 °C to higher temperatures (PHB, 200 °C; HHx=12 mol%, 140 °C) to explore their structure and thermal behavior. One of bands due to the CH 3 asymmetric stretching modes appears near 3010 cm -1 in the IR and Raman spectra of PHB and P(HB- co-HHx) at 20 °C. These frequencies of IR and Raman CH 3 asymmetric stretching bands are much higher than usual. These anomalous frequencies of the CH 3 asymmetric stretching bands together with the X-ray crystallographic structure of PHB have suggested that there is an inter- or intra-molecular C-H⋯O hydrogen bond between the C dbnd6 O group in one helical structure and the CH 3 group in the other helical structure in PHB and P(HB- co-HHx). The quantum chemical calculation of model compounds of PHB also has suggested the existence of C-H⋯O hydrogen bonds in PHB and P(HB- co-HHx). It is very likely that a chain of C-H⋯O hydrogen bond pairs link two parallel helical structures in the crystalline parts. The temperature-dependent IR and Raman spectral variations have revealed that the crystallinity of P(HB- co-HHx) (HHx=12 mol%) decreases gradually from a fairly low temperature (about 60 °C), while the crystallinity of PHB remains almost unchanged until just below its melting temperature. It has also been found from the IR and Raman studies that for both PHB and P(HB- co-HHx) the weakening of the C-H⋯O hydrogen bonds starts from just above room temperature, but the deformation of helical structures occurs after the weakening of the C-H⋯O hydrogen bonds advances to some extent.

  6. Non-innocent additives in a palladium(II)-catalyzed C-H bond activation reaction: insights into multimetallic active catalysts. (United States)

    Anand, Megha; Sunoj, Raghavan B; Schaefer, Henry F


    The role of a widely employed additive (AgOAc) in a palladium acetate-catalyzed ortho-C-H bond activation reaction has been examined using the M06 density functional theory. A new hetero-bimetallic Pd-(μ-OAc)3-Ag is identified as the most likely active species. This finding could have far-reaching implications with respect to the notion of the active species in palladium catalysis in the presence of other metal salt additives.

  7. Solvent-stabilized alkylrhodium(III) hydride complexes: a special mode of reversible C-H bond elimination involving an agostic intermediate (United States)

    Rybtchinski; Konstantinovsky; Shimon; Vigalok; Milstein


    Reaction of the complex [Rh(coe)2(solv)n]BF4 (coe=cyclooctene) with the phosphane 1-di-tert-butylphosphinomethyl-2,4,6-trimethylbenzene (1) results in selective C-H bond activation, yielding the spectroscopically characterized solvento complexes [(solv)nRhH(CH2C6H2(CH3)2[CH2P(tBu)2

  8. Promotional effects of chemisorbed oxygen and hydroxide in the activation of C-H and O-H bonds over transition metal surfaces (United States)

    Hibbitts, David; Neurock, Matthew


    Electronegative coadsorbates such as atomic oxygen (O*) and hydroxide (OH*) can act as Brønsted bases when bound to Group 11 as well as particular Group 8-10 metal surfaces and aid in the activation of X-H bonds. First-principle density functional theory calculations were carried out to systematically explore the reactivity of the C-H bonds of methane and surface methyl intermediates as well as the O-H bond of methanol directly and with the assistance of coadsorbed O* and OH* intermediates over Group 11 (Cu, Ag, and Au) and Group 8-10 transition metal (Ru, Rh, Pd, Os, Ir, and Pt) surfaces. C-H as well as O-H bond activation over the metal proceeds via a classic oxidative addition type mechanism involving the insertion of the metal center into the C-H or O-H bond. O* and OH* assist C-H and O-H activation over particular Group 11 and Group 8-10 metal surfaces via a σ-bond metathesis type mechanism involving the oxidative addition of the C-H or O-H bond to the metal along with a reductive deprotonation of the acidic C-H and O-H bond over the M-O* or M-OH* site pair. The O*- and OH*-assisted C-H activation paths are energetically preferred over the direct metal catalyzed C-H scission for all Group 11 metals (Cu, Ag, and Au) with barriers that are 0.4-1.5 eV lower than those for the unassisted routes. The barriers for O*- and OH*-assisted C-H activation of CH4 on the Group 8-10 transition metals, however, are higher than those over the bare transition metal surfaces by as much as 1.4 eV. The C-H activation of adsorbed methyl species show very similar trends to those for CH4 despite the differences in structure between the weakly bound methane and the covalently adsorbed methyl intermediates. The activation of the O-H bond of methanol is significantly promoted by O* as well as OH* intermediates over both the Group 11 metals (Cu, Ag, and Au) as well as on all Group 8-10 metals studied (Ru, Rh, Pd, Os, Ir, and Pt). The O*- and OH*-assisted CH3O-H barriers are 0.6 to 2

  9. Activation of C-H Bonds in Pt(+) + x CH4 Reactions, where x = 1-4: Identification of the Platinum Dimethyl Cation. (United States)

    Wheeler, Oscar W; Salem, Michelle; Gao, Amanda; Bakker, Joost M; Armentrout, P B


    Activation of C-H bonds in the sequential reactions of Pt(+) + x(CH4/CD4), where x = 1-4, have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy and theoretical calculations. Pt(+) cations are formed by laser ablation and exposed to controlled amounts of CH4/CD4 leading to [Pt,xC,(4x-2)H/D](+) dehydrogenation products. Irradiation of these products in the 400-2100 cm(-1) range leads to CH4/CD4 loss from the x = 3 and 4 products, whereas PtCH2(+)/PtCD2(+) products do not decompose at all, and x = 2 products dissociate only when formed from a higher order product. The structures of these complexes were explored theoretically at several levels of theory with three different basis sets. Comparison of the experimental and theoretical results indicate that the species formed have a Pt(CH3)2(+)(CH4)x-2/Pt(CD3)2(+)(CD4)x-2 binding motif for x = 2-4. Thus, reaction of Pt(+) with methane occurs by C-H bond activation to form PtCH2(+), which reacts with an additional methane molecule by C-H bond activation to form the platinum dimethyl cation. This proposed reaction mechanism is consistent with theoretical explorations of the potential energy surface for reactions of Pt(+) with one and two methane molecules.

  10. A general strategy for organocatalytic activation of C-H bonds via photoredox catalysis: direct arylation of benzylic ethers. (United States)

    Qvortrup, Katrine; Rankic, Danica A; MacMillan, David W C


    Direct C-H functionalization and arylation of benzyl ethers has been accomplished via photoredox organocatalysis. The productive merger of a thiol catalyst and a commercially available iridium photoredox catalyst in the presence of household light directly affords benzylic arylation products in good to excellent yield. The utility of this methodology is further demonstrated in direct arylation of 2,5-dihydrofuran to form a single regioisomer.

  11. Troponate/Aminotroponate Ruthenium-Arene Complexes: Synthesis, Structure, and Ligand-Tuned Mechanistic Pathway for Direct C-H Bond Arylation with Aryl Chlorides in Water. (United States)

    Dwivedi, Ambikesh D; Binnani, Chinky; Tyagi, Deepika; Rawat, Kuber S; Li, Pei-Zhou; Zhao, Yanli; Mobin, Shaikh M; Pathak, Biswarup; Singh, Sanjay K


    A series of water-soluble troponate/aminotroponate ruthenium(II)-arene complexes were synthesized, where O,O and N,O chelating troponate/aminotroponate ligands stabilized the piano-stool mononuclear ruthenium-arene complexes. Structural identities for two of the representating complexes were also established by single-crystal X-ray diffraction studies. These newly synthesized troponate/aminotroponate ruthenium-arene complexes enable efficient C-H bond arylation of arylpyridine in water. The unique structure-activity relationship in these complexes is the key to achieve efficient direct C-H bond arylation of arylpyridine. Moreover, the steric bulkiness of the carboxylate additives systematically directs the selectivity toward mono- versus diarylation of arylpyridines. Detailed mechanistic studies were performed using mass-spectral studies including identification of several key cyclometalated intermediates. These studies provided strong support for an initial cycloruthenation driven by carbonate-assisted deprotonation of 2-phenylpyridine, where the relative strength of η(6)-arene and the troponate/aminotroponate ligand drives the formation of cyclometalated 2-phenylpyridine Ru-arene species, [(η(6)-arene)Ru(κ(2)-C,N-phenylpyridine) (OH2)](+) by elimination of troponate/aminotroponate ligands and retaining η(6)-arene, while cyclometalated 2-phenylpyridine Ru-troponate/aminotroponate species [(κ (2)-troponate/aminotroponate)Ru(κ(2)-C,N-phenylpyridine)(OH2)2] was generated by decoordination of η(6)-arene ring during initial C-H bond activation of 2-phenylpyridine. Along with the experimental mass-spectral evidence, density functional theory calculation also supports the formation of such species for these complexes. Subsequently, these cycloruthenated products activate aryl chloride by facile oxidative addition to generate C-H arylated products.

  12. Interplay of Electronic Cooperativity and Exchange Coupling in Regulating the Reactivity of Diiron(IV)-oxo Complexes towards C-H and O-H Bond Activation. (United States)

    Ansari, Azaj; Ansari, Mursaleem; Singha, Asmita; Rajaraman, Gopalan


    Activation of inert C-H bonds such as those of methane are extremely challenging for chemists but in nature, the soluble methane monooxygenase (sMMO) enzyme readily oxidizes methane to methanol by using a diiron(IV) species. This has prompted chemists to look for similar model systems. Recently, a (μ-oxo)bis(μ-carboxamido)diiron(IV) ([Fe(IV)2 O(L)2 ](2+) L=N,N-bis-(3',5'-dimethyl-4'-methoxypyridyl-2'-methyl)-N'-acetyl-1,2-diaminoethane) complex has been generated by bulk electrolysis and this species activates inert C-H bonds almost 1000 times faster than mononuclear Fe(IV) =O species and at the same time selectively activates O-H bonds of alcohols. The very high reactivity and selectivity of this species is puzzling and herein we use extensive DFT calculations to shed light on this aspect. We have studied the electronic and spectral features of diiron {Fe(III) -μ(O)-Fe(III) }(+2) (complex I), {Fe(III) -μ(O)-Fe(IV) }(+3) (II), and {Fe(IV) -μ(O)-Fe(IV) }(+4) (III) complexes. Strong antiferromagnetic coupling between the Fe centers leads to spin-coupled S=0, S=3/2, and S=0 ground state for species I-III respectively. The mechanistic study of the C-H and O-H bond activation reveals a multistate reactivity scenario where C-H bond activation is found to occur through the S=4 spin-coupled state corresponding to the high-spin state of individual Fe(IV) centers. The O-H bond activation on the other hand, occurs through the S=2 spin-coupled state corresponding to an intermediate state of individual Fe(IV) centers. Molecular orbital analysis reveals σ-π/π-π channels for the reactivity. The nature of the magnetic exchange interaction is found to be switched during the course of the reaction and this offers lower energy pathways. Significant electronic cooperativity between two metal centers during the course of the reaction has been witnessed and this uncovers the reason behind the efficiency and selectivity observed. The catalyst is found to prudently choose the

  13. Hydroacylation of N=N bonds via aerobic C-H activation of aldehydes, and reactions of the products thereof


    Akhbar, A. R.


    The development of methods to construct new chemical bonds efficiently and selectively whilst minimising energy usage and waste production is of high importance in organic chemistry. Many current methods employ inefficient, costly and often toxic multi step protocols to generate new chemical bonds. The hydroacylation reaction is one method of reducing such inefficiencies. The development of an aerobic hydroacylation protocol in the Caddick group has recently allowed the functionalisation of a...

  14. Direct Synthesis of Protoberberine Alkaloids by Rh-Catalyzed C-H Bond Activation as the Key Step. (United States)

    Jayakumar, Jayachandran; Cheng, Chien-Hong


    A one-pot reaction of substituted benzaldehydes with alkyne-amines by a Rh-catalyzed C-H activation and annulation to afford various natural and unnatural protoberberine alkaloids is reported. This reaction provides a convenient route for the generation of a compound library of protoberberine salts, which recently have attracted great attention because of their diverse biological activities. In addition, pyridinium salt derivatives can also be formed in good yields from α,β-unsaturated aldehydes and amino-alkynes. This reaction proceeds with excellent regioselectivity and good functional group compatibility under mild reaction conditions by using O2 as the oxidant.

  15. Olefin cis-Dihydroxylation and Aliphatic C-H Bond Oxygenation by a Dioxygen-Derived Electrophilic Iron-Oxygen Oxidant. (United States)

    Chatterjee, Sayanti; Paine, Tapan Kanti


    Many iron-containing enzymes involve metal-oxygen oxidants to carry out O2-dependent transformation reactions. However, the selective oxidation of C-H and C=C bonds by biomimetic complexes using O2 remains a major challenge in bioinspired catalysis. The reactivity of iron-oxygen oxidants generated from an Fe(II)-benzilate complex of a facial N3 ligand were thus investigated. The complex reacted with O2 to form a nucleophilic oxidant, whereas an electrophilic oxidant, intercepted by external substrates, was generated in the presence of a Lewis acid. Based on the mechanistic studies, a nucleophilic Fe(II)-hydroperoxo species is proposed to form from the benzilate complex, which undergoes heterolytic O-O bond cleavage in the presence of a Lewis acid to generate an Fe(IV)-oxo-hydroxo oxidant. The electrophilic iron-oxygen oxidant selectively oxidizes sulfides to sulfoxides, alkenes to cis-diols, and it hydroxylates the C-H bonds of alkanes, including that of cyclohexane.

  16. A Cobalt(I) Pincer Complex with an η(2) -C(aryl)-H Agostic Bond: Facile C-H Bond Cleavage through Deprotonation, Radical Abstraction, and Oxidative Addition. (United States)

    Murugesan, Sathiyamoorthy; Stöger, Berthold; Pittenauer, Ernst; Allmaier, Günter; Veiros, Luis F; Kirchner, Karl


    The synthesis and reactivity of a Co(I) pincer complex [Co(ϰ(3) P,CH,P-P(CH)P(NMe) -iPr)(CO)2](+) featuring an η(2)-C(aryl)-H agostic bond is described. This complex was obtained by protonation of the Co(I) complex [Co(PCP(NMe) -iPr)(CO)2]. The Co(III) hydride complex [Co(PCP(NMe) -iPr)(CNtBu)2(H)](+) was obtained upon protonation of [Co(PCP(NMe) -iPr)(CNtBu)2]. Three ways to cleave the agostic C-H bond are presented. First, owing to the acidity of the agostic proton, treatment with pyridine results in facile deprotonation (C-H bond cleavage) and reformation of [Co(PCP(NMe) -iPr)(CO)2]. Second, C-H bond cleavage is achieved upon exposure of [Co(ϰ(3)P,CH,P-P(CH)P(NMe) -iPr)(CO)2](+) to oxygen or TEMPO to yield the paramagnetic Co(II) PCP complex [Co(PCP(NMe) -iPr)(CO)2](+). Finally, replacement of one CO ligand in [Co(ϰ(3) P,CH,P-P(CH)P(NMe) -iPr)(CO)2](+) by CNtBu promotes the rapid oxidative addition of the agostic η(2) -C(aryl)-H bond to give two isomeric hydride complexes of the type [Co(PCP(NMe) -iPr)(CNtBu)(CO)(H)](+).

  17. ${\\rm X-H}\\cdots {\\rm C}$ hydrogen bonds in -alkane-${\\rm HX} ({\\rm X} = {\\rm F, OH})$ complexes are stronger than ${\\rm C-H}· · ·{\\rm X}$ hydrogen bonds

    Indian Academy of Sciences (India)

    R Parajuli; E Arunan


    Computational study of ${\\rm X-H}\\cdots {\\rm C}$ and ${\\rm C-H}\\cdots{\\rm X}$ hydrogen bonds in n-alkane-${\\rm HX}$ complexes (${\\rm X} = {\\rm F,OH}$, alkane=propane, butane, pentane) has been carried out in this work. Ab initio and density functional theories were used for this study. For -alkane-${\\rm H}$2${\\rm O}$ complexes both ${\\rm O} \\cdots {\\rm H-C}$ and ${\\rm O-H}\\cdots {\\rm C}$ hydrogen bonded complex have been found, while for -alkane-${\\rm HF}$ complexes, our attempt to optimize ${\\rm F}\\cdots {\\rm H-C}$ ${\\rm H}$-bond was not successful. Like most of the hydrogen bonded systems, strong correlation between binding energy and stretching frequency of ${\\rm H-F}$ and ${\\rm O-H}$ stretching mode was observed. The values of electron density and Laplacian of electron density are within the accepted range for hydrogen bonds. In all these cases, ${\\rm X-H}\\cdots {\\rm C}$ hydrogen bonds are found to be stronger than ${\\rm C-H}\\cdots {\\rm X}$ hydrogen bonds.

  18. Pentachlorocyclopropane/base complexes: matrix isolation infrared spectroscopic and density functional study of C-H- - -N hydrogen bonds. (United States)

    Baker, Alexander B; Samet, Cindy; Lyon, Jonathan T; Andrews, Lester


    Hydrogen-bonded complexes of pentachlorocyclopropane with the bases acetonitrile, ammonia, monomethylamine, and dimethylamine have been isolated and characterized for the first time in argon matrices at 16 K. Coordination of the proton of pentachlorocyclopropane (Pccp) to the electron donor (N) of the base was evidenced by red shifts of the CH stretching mode. These shifts, which range from 22 to 170 cm(-1), increase in the order CH3CN, NH3, (CH3)NH2, and (CH3)2NH. Density functional theory (DFT) calculations at the B3LYP level agree well with experiment and support the formation of 1:1 complexes of Pccp/base. Distinct changes were observed in ring modes as well as CCl and CCl2 modes. The hydrogen bond energy of the complexes varies from 2.95 to 4.22 kcal/mol and is stronger than our previously studied bromocyclopropane-ammonia complex (2.35 kcal/mol, MP2).

  19. Thermochemistry of C7H16 to C10H22 alkane isomers: primary, secondary, and tertiary C-H bond dissociation energies and effects of branching. (United States)

    Hudzik, Jason M; Bozzelli, Joseph W; Simmie, John M


    Standard enthalpies of formation (ΔH°f 298) of methyl, ethyl, primary and secondary propyl, and n-butyl radicals are evaluated and used in work reactions to determine internal consistency. They are then used to calculate the enthalpy of formation for the tert-butyl radical. Other thermochemical properties including standard entropies (S°(T)), heat capacities (Cp(T)), and carbon-hydrogen bond dissociation energies (C-H BDEs) are reported for n-pentane, n-heptane, 2-methylhexane, 2,3-dimethylpentane, and several branched higher carbon number alkanes and their radicals. ΔH°f 298 and C-H BDEs are calculated using isodesmic work reactions at the B3LYP (6-31G(d,p) and 6-311G(2d,2p) basis sets), CBS-QB3, CBS-APNO, and G3MP2B3 levels of theory. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level for contributions to entropy and heat capacities. Enthalpy calculations for these hydrocarbon radical species are shown to have consistency with the CBS-QB3 and CBS-APNO methods using all work reactions. Our recommended ideal gas phase ΔH°f 298 values are from the average of all CBS-QB3, CBS-APNO, and for G3MP2B3, only where the reference and target radical are identical types, and are compared with literature values. Calculated values show agreement between the composite calculation methods and the different work reactions. Secondary and tertiary C-H bonds in the more highly branched alkanes are shown to have bond energies that are several kcal mol(-1) lower than the BDEs in corresponding smaller molecules often used as reference species. Entropies and heat capacities are calculated and compared to literature values (when available) when all internal rotors are considered.

  20. Experimental charge density and neutron structural study of cis-HMn(CO){sub 4}PPh{sub 3}: Comprehensive analysis of chemical bonding and evidence for a C-H{hor_ellipsis}H-Mn hydrogen bond

    Energy Technology Data Exchange (ETDEWEB)

    Abramov, Y.A.; Brammer, L. [Univ. of Missouri, St. Louis, MO (United States). Dept. of Chemistry; Klooster, W.T.; Bullock, R.M. [Brookhaven National Lab., Upton, NY (United States). Chemistry Dept.


    The structure and bonding in cis-HMn(CO){sub 4}PPh{sub 3} have been studied by low-temperature neutron and high-resolution X-ray diffraction, the latter study using a charge-coupled device (CCD) area detector. A charge density analysis, including the deformation density, a full topological analysis of {minus}{del}{sup 2}{rho}, has been conducted. The electrostatic component of the H{sup {delta}+}{hor_ellipsis}H{sup {delta}{minus}} interaction energy is calculated to be 5.7 kcal/mol from the experimental data. This electrostatic evidence coupled with the geometry C-H{hor_ellipsis}H 129.0(2){degree} and H{hor_ellipsis}H-Mn 126.5(1){degree} and the identification of an H{hor_ellipsis}H bond path in the charge density distribution strongly supports the characterization of this interaction as an intramolecular C-H{hor_ellipsis}H-Mn hydrogen bond. Both the deformation density and the topological study clearly illustrate the {sigma}-donor nature of both the H-Mn and Ph{sub 3}P-Mn interactions and the {sigma}-donor/{pi}-acceptor nature of the manganese-carbonyl bonds. The topological study further confirms the decrease in C-O bond order upon coordination to the metal and demonstrates for the first time by this method that the metal-ligand bonds, although showing characteristics of a closed-shell interaction, do have a significant dative covalent component to the bond. The latter is reinforced by a study of the derived Mn d-orbital populations, in which populations of the d{sub z{sup 2}} and d{sub x{sup 2}{minus}y{sup 2}} orbitals are significantly higher than would be predicted by a simple crystal field theory model of metal-ligand bonding.

  1. Ligand versus Complex: C-F and C-H Bond Activation of Polyfluoroaromatics at a Cyclic (Alkyl)(Amino)Carbene. (United States)

    Paul, Ursula S D; Radius, Udo


    C-F and C-H bond activation reactions of polyfluoroaromatics at the cyclic (alkyl)(amino)carbene (cAAC) cAAC(methyl) (1) are reported. Studies on the C-F bond activation using the cAAC-stabilized nickel(0) complex [Ni(cAAC(methyl) )2 ] (2) have shown that 2 does not react with fluorinated arenes. However, these investigations led to the observation of C-F bond cleavage of perfluorinated arenes by the carbene ligand cAAC(methyl) (1) itself. The reaction of 1 with C6 F6 , C6 F5 -C6 F5 , C6 F5 -CF3 , and C5 F5 N afforded the insertion products of cAAC into one of the C-F bonds of the substrate, that is, the C-F bond activation products (cAAC(methyl) )F(Ar(f) ) (Ar(f) =C6 F5 4 a, C6 F4 -C6 F5 4 b, C6 F4 -CF3 4 c, C5 F4 N 4 d). These products decompose readily upon heating to 80 °C within a few hours in solution with formation of ionic iminium salts [(cAAC(methyl) )(Ar(f) )][X] 6 a-d or neutral alkenyl perfluoroaryl imine compounds 7 a-d. The compounds (cAAC(methyl) )F(Ar(f) ) 4 a-d readily transfer fluoride, which has been exemplified by the fluoride transfer of all compounds using BF3 etherate as fluoride acceptor. Fluoride transfer has also been achieved starting from (cAAC(methyl) )F(C6 F4 -CF3 ) (4 c) or (cAAC(methyl) )F(C5 F4 N) (4 d) to other selected substrates such as trimethylchlorosilane, benzoyl chloride and tosyl chloride. Instead of C-F bond activation, insertion of the cAAC into the C-H bond was observed if 1 was treated with the partially fluorinated arenes C6 F5 H, 1,2,4,5-C6 F4 H2 , 1,3,5-C6 F3 H3 , and 1,3-C6 F2 H4 . The compounds (cAAC(methyl) )H(Ar(f) ) (Ar(f) =C6 F5 12 e, 2,3,5,6-C6 F4 H 12 f, 2,4,6-C6 F3 H2 12 g and 2,6-C6 F2 H3 12 h) have been isolated in good yields and have been characterized including X-ray analysis. Fluorobenzene C6 FH5 (pKa ≈37), the least C-H acidic fluoroarene used in this study, does not react. In order to investigate the scope and limitations of this type of cAAC C-H bond activation

  2. Crystal and molecular structure of ( r-2, c-4)-3-benzyl-2,4,5,5-tetraphenyl1,3-thiazolidine, intramolecular C-H⋯S hydrogen bonds (United States)

    Domagała, Małgorzata; Grabowski, Sławomir J.; Urbaniak, Katarzyna; Mlostoń, Grzegorz


    The crystal and molecular structures of ( r-2, c-4)-3-benzyl-2,4,5,5-tetraphenyl-1,3-thiazolidine are investigated showing the existence of C(sp 2)-H⋯S and C(sp 2)-H⋯N intramolecular contacts. The analysis of geometrical parameters shows that C-H⋯S contacts may be treated as hydrogen bonds but C-H⋯N do not fulfil the geometrical criteria of the existence of H-bonds. The B3LYP/6-311+G* single point calculations were performed to obtain wave functions applied later for 'atoms in molecules' (AIM) study. The analysis of bond critical points based on the Bader theory (AIM) supports the existence of intramolecular C-H⋯S H-bonds.


    Institute of Scientific and Technical Information of China (English)

    Jing Xu; Yu-hong Ma; Jing-yi Xie; Wan-tai Yang


    A one-step process to introduce both the aromatic and aliphatic primary amino groups with high chemoselectivity was developed.Triplet state acetone abstracts the hydrogen atoms from both the C--H bond of the polymeric film substrate and the OH bond of phenol which is the building block and the amino group carrier.As a result,two kinds of free radicals,confined carbon-centered chain radicals of the polymer substrate and mobile oxygen-centered phenoxy radicals,were generated.Then the C-O bonds were formed by the coupling reaction between these two kinds of free radicals,p-Tyramine and p-aminophenol were used as amino carriers.The successful introduction of amino groups onto LDPE,BOPP and PET film substrates was demonstrated by measurements of water contract angle (CA),ultraviolet spectra (UV),X-ray photoelectron spectroscopy (XPS) and fluorescent microscopy.The processing factors,such as the UV-light intensity and irradiation time,concentrations of p-tyramine and p-aminophenol,and the ratio of acetone/water were investigated.The optimized process parameters are as follows:UV light intensity 9500 μW/cm2; irradiation time 18 min for BOPP and LDPE,22 rmin for PET; the ratio of acetone/water =1; and concentration ofp-tyramine and p-aminophenol 15% for BOPP and LDPE,1% for PET.Based on the UV absorbance,the amino groups on the polymeric substrates were estimated to be in the range of 6.3 x 10-6-9.5 x 10-6 mmol/mm2.

  4. Reactivity and selectivity patterns in hydrogen atom transfer from amino acid C-H bonds to the cumyloxyl radical: polar effects as a rationale for the preferential reaction at proline residues. (United States)

    Salamone, Michela; Basili, Federica; Bietti, Massimo


    Absolute rate constants for hydrogen atom transfer (HAT) from the C-H bonds of N-Boc-protected amino acids to the cumyloxyl radical (CumO(•)) were measured by laser flash photolysis. With glycine, alanine, valine, norvaline, and tert-leucine, HAT occurs from the α-C-H bonds, and the stability of the α-carbon radical product plays a negligible role. With leucine, HAT from the α- and γ-C-H bonds was observed. The higher kH value measured for proline was explained in terms of polar effects, with HAT that predominantly occurs from the δ-C-H bonds, providing a rationale for the previous observation that proline residues represent favored HAT sites in the reactions of peptides and proteins with (•)OH. Preferential HAT from proline was also observed in the reactions of CumO(•) with the dipeptides N-BocProGlyOH and N-BocGlyGlyOH. The rate constants measured for CumO(•) were compared with the relative rates obtained previously for the corresponding reactions of different hydrogen-abstracting species. The behavior of CumO(•) falls between those observed for the highly reactive radicals Cl(•) and (•)OH and the significantly more stable Br(•). Taken together, these results provide a general framework for the description of the factors that govern reactivity and selectivity patterns in HAT reactions from amino acid C-H bonds.

  5. Direct evidence for preferential {beta} C-H bond cleavage resulting from 248 nm photolysis of the n-propyl radical using selectively-deuterated 1-bromopropane precursors

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Z.; Mathews, M.G.; Koplitz, B. [Tulane Univ., New Orleans, LA (United States)


    A series of selectively deuterated 1-bromopropane precursors have been used to study site-specific photolysis in the n-propyl radical. A two-color photolysis approach (222 nm followed by 248 nm radiation) is used to create an intermediate photofragment and produce an H or a D atom, which is detected by 1 + 1 resonance ionization through Lyman-{alpha}. Target precursors are BrCH{sub 2}CD{sub 2}CD{sub 3}, BrCD{sub 2}CH{sub 2}CD{sub 3}, and BrCD{sub 2}CD{sub 2}CH{sub 3} as well as BrCD{sub 2}CH{sub 2}CH{sub 3}, BrCH{sub 2}CD{sub 2}CH{sub 3}, and BrCH{sub 2}CH{sub 2}CD{sub 3}. The `enhanced` H (or D) atom signals clearly demonstrate that C-H (or C-D) bond cleavage at the {beta} position is strongly favored. The net enhancement process undoubtedly involves photolysis of an intermediate, almost certainly the n-propyl radical. A comparison with systems involving ethyl and isopropyl radical photolysis is also presented. 14 refs., 4 figs.

  6. Size-extensive wave functions for quantum Monte Carlo: A linear scaling generalized valence bond approach

    NARCIS (Netherlands)

    Fracchia, F.; Filippi, C.; Amovilli, C.


    We propose a new class of multideterminantal Jastrow–Slater wave functions constructed with localized orbitals and designed to describe complex potential energy surfaces of molecular systems for use in quantum Monte Carlo (QMC). Inspired by the generalized valence bond formalism, we elaborate a coup

  7. The selective activation of a C-F bond with an auxiliary strong Lewis acid: a method to change the activation preference of C-F and C-H bonds. (United States)

    Wang, Lin; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter


    The selective activation of the C-F bonds in substituted (2,6-difluorophenyl)phenylimines (2,6-F2H3C6-(C[double bond, length as m-dash]NH)-n'-R-C6H4 (n' = 2, R = H (1); n' = 2, R = Me (2); n' = 4, R = tBu (3))) by Fe(PMe3)4 with an auxiliary strong Lewis acid (LiBr, LiI, or ZnCl2) was explored. As a result, iron(ii) halides ((H5C6-(C[double bond, length as m-dash]NH)-2-FH3C6)FeX(PMe3)3 (X = Br (8); Cl (9)) and (n-RH4C6-(C[double bond, length as m-dash]NH)-2'-FH3C6)FeX(PMe3)3 (n = 2, R = Me, X = Br (11); n = 4, R = tBu, X = I (12))) were obtained. Under similar reaction conditions, using LiBF4 instead of LiBr or ZnCl2, the reaction of (2,6-difluorophenyl)phenylimine with Fe(PMe3)4 afforded an ionic complex [(2,6-F2H3C6-(C[double bond, length as m-dash]NH)-H4C6)Fe(PMe3)4](BF4) (10) via the activation of a C-H bond. The method of C-F bond activation with an auxiliary strong Lewis acid is appropriate for monofluoroarylmethanimines. Without the Lewis acid, iron(ii) hydrides ((2-RH4C6-(C[double bond, length as m-dash]NH)-2'-FH3C6)FeH(PMe3)3 (R = H (13); Me (14))) were generated from the reactions of Fe(PMe3)4 with the monofluoroarylmethanimines (2-FH4C6-(C[double bond, length as m-dash]NH)-2'-RC6H4 (R = H (4); Me (5))); however, in the presence of ZnCl2 or LiBr, iron(ii) halides ((2-RH4C6-(C[double bond, length as m-dash]NH)-H4C6)FeX(PMe3)3 (R = H, X = Cl (15); R = Me, X = Br (16))) could be obtained through the activation of a C-F bond. Furthermore, a C-F bond activation with good regioselectivity in (pentafluorophenyl)arylmethanimines (F5C6-(C[double bond, length as m-dash]NH)-2,6-Y2C6H3 (Y = F (6); H (7))) could be realized in the presence of ZnCl2 to produce iron(ii) chlorides ((2,6-Y2H3C6-(C[double bond, length as m-dash]NH)-F4C6)FeCl(PMe3)3 (Y = F (17); H (18))). This series of iron(ii) halides could be used to catalyze the hydrosilylation reaction of aldehydes. Due to the stability of iron(ii) halides to high temperature, the reaction mixture was allowed to be

  8. Cocrystals of 1,4-diethynylbenzene with 1,3-diacetylbenzene and benzene-1,4-dicarbaldehyde exhibiting strong nonconventional alkyne-carbonyl C-H...O hydrogen bonds between the components. (United States)

    Bosch, Eric


    Weak interactions between organic molecules are important in solid-state structures where the sum of the weaker interactions support the overall three-dimensional crystal structure. The sp-C-H...N hydrogen-bonding interaction is strong enough to promote the deliberate cocrystallization of a series of diynes with a series of dipyridines. It is also possible that a similar series of cocrystals could be formed between molecules containing a terminal alkyne and molecules which contain carbonyl O atoms as the potential hydrogen-bond acceptor. I now report the crystal structure of two cocrystals that support this hypothesis. The 1:1 cocrystal of 1,4-diethynylbenzene with 1,3-diacetylbenzene, C10H6·C10H10O2, (1), and the 1:1 cocrystal of 1,4-diethynylbenzene with benzene-1,4-dicarbaldehyde, C10H6·C8H6O2, (2), are presented. In both cocrystals, a strong nonconventional ethynyl-carbonyl sp-C-H...O hydrogen bond is observed between the components. In cocrystal (1), the C-H...O hydrogen-bond angle is 171.8 (16)° and the H...O and C...O hydrogen-bond distances are 2.200 (19) and 3.139 (2) Å, respectively. In cocrystal (2), the C-H...O hydrogen-bond angle is 172.5 (16)° and the H...O and C...O hydrogen-bond distances are 2.25 (2) and 3.203 (2) Å, respectively.

  9. Binding to Redox-Inactive Alkali and Alkaline Earth Metal Ions Strongly Deactivates the C-H Bonds of Tertiary Amides toward Hydrogen Atom Transfer to Reactive Oxygen Centered Radicals. (United States)

    Salamone, Michela; Carboni, Giulia; Mangiacapra, Livia; Bietti, Massimo


    The effect of alkali and alkaline earth metal ions on the reactions of the cumyloxyl radical (CumO(•)) with N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) was studied by laser flash photolysis. In acetonitrile, a >2 order of magnitude decrease in the rate constant for hydrogen atom transfer (HAT) from the C-H bonds of these substrates (kH) was measured after addition of Li(+). This behavior was explained in terms of a strong interaction between Li(+) and the oxygen atom of both DMF and DMA that increases the extent of positive charge on the amide, leading to C-H bond deactivation toward HAT to the electrophilic radical CumO(•). Similar effects were observed after addition of Ca(2+), which was shown to strongly bind up to four equivalents of the amide substrates. With Mg(2+), weak C-H deactivation was observed for the first two substrate equivalents followed by stronger deactivation for two additional equivalents. No C-H deactivation was observed in DMSO after addition of Li(+) and Mg(2+). These results point toward the important role played by metal ion Lewis acidity and solvent Lewis basicity, indicating that C-H deactivation can be modulated by varying the nature of the metal cation and solvent and allowing for careful control over the HAT reactivity of amide substrates.

  10. The amide C-N bond of isatins as the directing group and the internal oxidant in Ru-catalyzed C-H activation and annulation reactions: access to 8-amido isocoumarins. (United States)

    Kaishap, Partha Pratim; Sarma, Bipul; Gogoi, Sanjib


    The N-O, N-N and O-O bonds are the frequently used internally oxidative directing groups used in various redox-neutral coupling reactions. The sole use of the C-N bond as the oxidizing directing group was reported recently by Li X. and co-workers for the Rh(iii)-catalyzed C-H activation of phenacyl ammonium salts. Herein, we report the use of the amide C-N bond of isatins as the oxidizing directing group for the Ru(ii)-catalyzed redox-neutral C-H activation and annulation reactions with alkynes which afford 8-amido isocoumarins. The reaction also features excellent regioselectivity with alkyl aryl substituted alkynes.

  11. Metalloporphyrin-mediated asymmetric nitrogen-atom transfer to hydrocarbons: aziridination of alkenes and amidation of saturated C-H bonds catalyzed by chiral ruthenium and manganese porphyrins. (United States)

    Liang, Jiang-Lin; Huang, Jie-Sheng; Yu, Xiao-Qi; Zhu, Nianyong; Che, Chi-Ming


    Chiral metalloporphyrins [Mn(Por*)(OH)(MeOH)] (1) and [Ru(Por*)(CO)(EtOH)] (2) catalyze asymmetric aziridination of aromatic alkenes and asymmetric amidation of benzylic hydrocarbons to give moderate enantiomeric excesses. The mass balance in these nitrogen-atom-transfer processes has been examined. With PhI=NTs as the nitrogen source, the aziridination of styrenes, trans-stilbene, 2-vinylnaphthalene, indene, and 2,2-dimethylchromene catalyzed by complex 1 or 2 resulted in up to 99 % substrate conversions and up to 94 % aziridine selectivities, whereas the amidation of ethylbenzenes, indan, tetralin, 1-, and 2-ethylnaphthalene catalyzed by complex 2 led to substrate conversions of up to 32 % and amide selectivities of up to 91 %. Complex 1 or 2 can also catalyze the asymmetric amidation of 4-methoxyethylbenzene, tetralin, and 2-ethylnaphthalene with "PhI(OAc)(2) + NH(2)SO(2)Me", affording the N-substituted methanesulfonamides in up to 56 % ee with substrate conversions of up to 34 % and amide selectivities of up to 92 %. Extension of the "complex 1 + PhI=NTs" or "complex 1 + PhI(OAc)(2) + NH(2)R (R=Ts, Ns)" amidation protocol to a steroid resulted in diastereoselective amidation of cholesteryl acetate at the allylic C-H bonds at C-7 with substrate conversions of up to 49 % and amide selectivities of up to 90 % (alpha:beta ratio: up to 4.2:1). An aziridination- and amidation-active chiral bis(tosylimido)ruthenium(VI) porphyrin, [Ru(Por*)(NTs)(2)] (3), and a ruthenium porphyrin aziridine adduct, [Ru(Por*)(CO)(TsAz)] (4, TsAz=N-tosyl-2- (4-chlorophenyl)aziridine), have been isolated from the reaction of 2 with PhI=NTs and N-tosyl-2-(4-chlorophenyl)aziridine, respectively. The imidoruthenium porphyrin 3 could be an active species in the aziridination or amidation catalyzed by complex 2 described above. The second-order rate constants for the reactions of 3 with styrenes, 2-vinylnaphthalene, indene, ethylbenzenes, and 2-ethylnaphthalene range from 3.7-42.5x10(-3) dm(3

  12. Strength of C-H Bonds at Nitrogen a-Position: Implication for Metabolic Stability of Nitrogen-containing Drug Molecules

    Institute of Scientific and Technical Information of China (English)

    MENG Xiang-Ming; ZOU Lu-Feng; XIE Miao; FU Yao


    The available experimental αC-H BDEs of a variety of amine-containing molecules were examined by using the G3B3 and CBS-Q methods. The verified values were employed to benchmark and calibrate the density functional theory methods. It was found that the (U)BHandH/6-311++G(2df, 2p)//(U)B3LYP/6-31G(d) method was a fast and accurate method for calculating C-H BDEs at nitrogen a-positions. By using the newly benchmarked BHandH method, the aC-H BDEs in a number of nitrogen-containing drug molecules were calculated, where a dramatic variation of the αC-H BDEs was discovered. To understand this variation, the effects of mono- and double-substitution at both carbon and nitrogen atoms on the aC-H BDEs were systematically studied. The origin of the substitution effects was thoroughly discussed in terms of four categories of substituents.

  13. Forced twin-chair conformation in 7-benzoyl- and 7-phenylacetyl-r-2,c-4,t-6,t-8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonanes with 1,3-diaxial phenyl groups in the piperidine ring: single- and double-layered supramolecular sheets built from C-H...O and C-H...pi(arene) hydrogen bonds. (United States)

    Sakthivel, Chinniah; Jeyaraman, Ramasubbu


    The crystal structures of 7-benzoyl-r-2,c-4,t-6,t-8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonane, C(38)H(33)NOS, (I), and r-2,c-4,t-6,t-8-tetraphenyl-7-phenylacetyl-3-thia-7-azabicyclo[3.3.1]nonane [systematic name: 2-phenyl-1-(r-2,c-4,t-6,t-8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonan-7-yl)ethanone], C(39)H(35)NOS, (II), both reveal a forced twin-chair conformation with the 1,3-diaxial phenyl groups in the piperidine ring, and flattening at the N-atom end of the piperidine ring of the bicyclic system. In the crystal structure of (I), molecules are linked into sheets by a combination of two weak C-H...O and one C-H...pi(arene) hydrogen bond, while in the crystal structure of (II), the molecules extend into double-layered sheets assisted by three C-H...pi(arene) hydrogen bonds.

  14. Critical behavior of the random-bond Ashkin-Teller model: A Monte Carlo study (United States)

    Wiseman, Shai; Domany, Eytan


    The critical behavior of a bond-disordered Ashkin-Teller model on a square lattice is investigated by intensive Monte Carlo simulations. A duality transformation is used to locate a critical plane of the disordered model. This critical plane corresponds to the line of critical points of the pure model, along which critical exponents vary continuously. Along this line the scaling exponent corresponding to randomness φ=(α/ν) varies continuously and is positive so that the randomness is relevant, and different critical behavior is expected for the disordered model. We use a cluster algorithm for the Monte Carlo simulations based on the Wolff embedding idea, and perform a finite size scaling study of several critical models, extrapolating between the critical bond-disordered Ising and bond-disordered four-state Potts models. The critical behavior of the disordered model is compared with the critical behavior of an anisotropic Ashkin-Teller model, which is used as a reference pure model. We find no essential change in the order parameters' critical exponents with respect to those of the pure model. The divergence of the specific heat C is changed dramatically. Our results favor a logarithmic type divergence at Tc, C~lnL for the random-bond Ashkin-Teller and four-state Potts models and C~ln lnL for the random-bond Ising model.

  15. A regioselective synthesis of benzopinacolones through aerobic dehydrogenative α-arylation of the tertiary sp3 C-H bond of 1,1-diphenylketones with aromatic and heteroaromatic compounds. (United States)

    More, Nagnath Yadav; Jeganmohan, Masilamani


    A regioselective synthesis of symmetrical and unsymmetrical benzopinacolones through aerobic dehydrogenative α-arylation at the tertiary sp(3) C-H bond of substituted 1,1-diphenylketones with aromatic and heteroaromatic compounds, in the presence of K2S2O8 in CF3COOH at room temperature, is described. The reaction is proposed to go via a carbocation intermediate, which could be generated directly from cleavage of the sp(3) C-H bond of 1,1-diphenylketone. Subsequent α-arylation was achieved at the methene sp(3) carbon atom of the substituted ketone. A variety of substituted aromatic and heteroaromatic compounds were compatible with this reaction. In addition, benzopinacolones were converted into sterically hindered, tetrasubstituted alkenes and polycyclic aromatic compounds.

  16. Birge-Sponer Estimation of the C-H Bond Dissociation Energy in Chloroform Using Infrared, Near-Infrared, and Visible Absorption Spectroscopy: An Experiment in Physical Chemistry (United States)

    Myrick, M. L.; Greer, A. E.; Nieuwland, A. A.; Priore, R. J.; Scaffidi, J.; Andreatta, Danielle; Colavita, Paula


    The fundamental and overtone vibrational absorption spectroscopy of the C-H unit in CHCl[subscript 3] is measured for transitions from the v = 0 energy level to v = 1 through v = 5 energy levels. The energies of the transitions exhibit a linearly-decreasing spacing between adjacent vibrational levels as the vibrational quantum number increases.…

  17. Using a non-spin flip model to rationalize the irregular patterns observed in the activation of the C-H and Si-H bonds of small molecules by CpMCO (M = Co, Rh) complexes. (United States)

    Castro, Guadalupe; Colmenares, Fernando


    The activation of the C-H and Si-H bonds of CH(CH3)3 and SiH(CH3)3 molecules by organometallic compounds CpMCO (M = Co, Rh) has been investigated through DFT and CASSCF-MRMP2 calculations. In particular, we have analyzed the pathways joining the lowest-lying triplet and singlet states of the reactants with the products arising from the insertion of the metal atom into the C-H or Si-H bonds of the organic molecules. Channels connecting the reactants with the inserted structure Cp(CO)H-M-C(CH3)3 through the oxidative addition of the C-H bond of the organic molecule to the metal fragment were found only for the reaction CpRhCO + CH(CH3)3. However, inserted structures could also be obtained for the interactions of SiH(CH3)3 with CpCoCO and CpRhCO by two sequential reactions involving the formation and rebounding of the radical fragments Cp(CO)H-M + Si(CH3)3. According to this two-step reaction scheme, the complex CpCoCO is unable to activate the C-H bond of the CH(CH3)3 molecule due to the high energy at which the radical fragments Cp(CO)H-M + C(CH3)3 are located. The picture attained for these interactions is consistent with the available experimental data for this kind of reaction and allows rationalization of the differences in the reactivity patterns determined for them without using spin-flip models, as has been proposed in previous studies.

  18. An elusive hydridoaluminum(I) complex for facile C-H and C-O bond activation of ethers and access to its isolable hydridogallium(I) analogue: syntheses, structures, and theoretical studies. (United States)

    Tan, Gengwen; Szilvási, Tibor; Inoue, Shigeyoshi; Blom, Burgert; Driess, Matthias


    The reaction of AlBr3 with 1 molar equiv of the chelating bis(N-heterocyclic carbene) ligand bis(N-Dipp-imidazole-2-ylidene)methylene (bisNHC, 1) affords [(bisNHC)AlBr2](+)Br(-) (2) as an ion pair in high yield, representing the first example of a bisNHC-Al(III) complex. Debromination of the latter with 1 molar equiv of K2Fe(CO)4 in tetrahydrofuran (THF) furnishes smoothly, in a redox reaction, the (bisNHC)(Br)Al[Fe(CO)4] complex 3, in which the Al(I) center is stabilized by the Fe(CO)4 moiety through Al(I):→Fe(0) coordination. Strikingly, the Br/H ligand exchange reactions of 3 using potassium hydride as a hydride source in THF or tetrahydropyran (THP) do not yield the anticipated hydridoaluminum(I) complex (bisNHC)Al(H)[Fe(CO)4] (4a) but instead lead to (bisNHC)Al(2-cyclo-OC4H7)[Fe(CO)4] (4) and (bisNHC)Al(2-cyclo-OC5H9)[Fe(CO)4] (5), respectively. The latter are generated via C-H bond activation at the α-carbon positions of THF and THP, respectively, in good yields with concomitant elimination of dihydrogen. This is the first example whereby a low-valent main-group hydrido complex facilitates metalation of sp(3) C-H bonds. Interestingly, when K[BHR3] (R = Et, sBu) is employed as a hydride source to react with 3 in THF, the reaction affords (bisNHC)Al(OnBu)[Fe(CO)4] (6) as the sole product through C-O bond activation and ring opening of THF. The mechanisms for these novel C-H and C-O bond activations mediated by the elusive hydridoaluminum(I) complex 4a were elucidated by density functional theory (DFT) calculations. In contrast, the analogous hydridogallium(I) complex (bisNHC)Ga(H)[Fe(CO)4] (9) can be obtained directly in high yield by the reaction of the (bisNHC)Ga(Cl)[Fe(CO)4] precursor 8 with 1 molar equiv of K[BHR3] (R = Et, sBu) in THF at room temperature. The isolation of 9 and its inertness toward cyclic ethers might be attributed to the higher electronegativity of gallium versus aluminum. The stronger Ga(I)-H bond, in turn, hampers α-C-H metalation

  19. (18)F-Fluorination of Unactivated C-H Bonds in Branched Aliphatic Amino Acids: Direct Synthesis of Oncological Positron Emission Tomography Imaging Agents. (United States)

    Nodwell, Matthew B; Yang, Hua; Čolović, Milena; Yuan, Zheliang; Merkens, Helen; Martin, Rainer E; Bénard, François; Schaffer, Paul; Britton, Robert


    A mild and selective photocatalytic C-H (18)F-fluorination reaction has been developed that provides direct access to (18)F-fluorinated amino acids. The biodistribution and uptake of three (18)F-labeled leucine analogues via LAT1 mediated transport in several cancer cell lines is reported. Positron emission tomography imaging of mice bearing PC3 (prostate) or U87 (glioma) xenografts using 5-[(18)F]-fluorohomoleucine showed high tumor uptake and excellent tumor visualization, highlighting the utility of this strategy for rapid tracer discovery for oncology.

  20. Intermolecular interactions involving C-H bonds, 3, Structure and energetics of the interaction between CH{sub 4} and CN{sup {minus}}

    Energy Technology Data Exchange (ETDEWEB)

    Novoa, J.J.; Whangbo, Myung-Hwan [North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemistry; Williams, J.M. [Argonne National Lab., IL (United States)


    On the basis of SCF and single reference MP2 calculations, the full potential energy surface of the interaction between CH{sub 4} and CN{sup {minus}} was studied using extended basis sets of up to near Hartree-Fock limit quality. Colinear arrangements C-N{sup {minus}}{hor_ellipsis}H-CH{sub 3} and N-C{sup {minus}}{hor_ellipsis}H-CH{sub 3} are found to be the only two energy minima. The binding energies of these two structures are calculated to be 2.5 and 2.1 kcal/mol, respectively, at the MP2 level. The full vibrational analyses of two structures show a red shift of about 30 cm{sup {minus}1} for the v{sub s} C-H stretching.

  1. Formation of a ruthenium(IV)-oxo complex by electron-transfer oxidation of a coordinatively saturated ruthenium(II) complex and detection of oxygen-rebound intermediates in C-H bond oxygenation. (United States)

    Kojima, Takahiko; Nakayama, Kazuya; Ikemura, Kenichiro; Ogura, Takashi; Fukuzumi, Shunichi


    A coordinatively saturated ruthenium(II) complex having tetradentate tris(2-pyridylmethyl)amine (TPA) and bidentate 2,2'-bipyridine (bpy), [Ru(TPA)(bpy)](2+) (1), was oxidized by a Ce(IV) ion in H(2)O to afford a Ru(IV)-oxo complex, [Ru(O)(H(+)TPA)(bpy)](3+) (2). The crystal structure of the Ru(IV)-oxo complex 2 was determined by X-ray crystallography. In 2, the TPA ligand partially dissociates to be in a facial tridentate fashion and the uncoordinated pyridine moiety is protonated. The spin state of 2, which showed paramagnetically shifted NMR signals in the range of 60 to -20 ppm, was determined to be an intermediate spin (S = 1) by the Evans' method with (1)H NMR spectroscopy in acetone-d(6). The reaction of 2 with various oraganic substrates in acetonitrile at room temperature afforded oxidized and oxygenated products and a solvent-bound complex, [Ru(H(+)TPA)(bpy)(CH(3)CN)], which is intact in the presence of alcohols. The oxygenation reaction of saturated C-H bonds with 2 proceeds by two-step processes: the hydrogen abstraction with 2, followed by the dissociation of the alcohol products from the oxygen-rebound complexes, Ru(III)-alkoxo complexes, which were successfully detected by ESI-MS spectrometry. The kinetic isotope effects in the first step for the reaction of dihydroanthrathene (DHA) and cumene with 2 were determined to be 49 and 12, respectively. The second-order rate constants of C-H oxygenation in the first step exhibited a linear correlation with bond dissociation energies of the C-H bond cleavage.

  2. Investigation of C-H...O=C and N-H...OC hydrogen-bonding interactions in crystalline thymine by DFT calculations of O-17, N-14 and H-2 NQR parameters. (United States)

    Mirzaei, Mahmoud; Hadipour, Nasser L; Ahmadi, Kamran


    A computational study at the level of density functional theory (DFT) was carried out to investigate C-H...O=C and N-H...O=C hydrogen-bonding interactions (HBs) in the real crystalline cluster of thymine by O-17, N-14 and H-2 calculated nuclear quadrupole resonance (NQR) parameters. To perform the calculations, a hydrogen-bonded pentameric cluster of thymine was created using X-ray coordinates where the hydrogen atoms positions are optimized and the electric field gradient (EFG) tensors were calculated for the target molecule. Additional EFG calculations were also performed for crystalline monomer and an optimized isolated gas-phase thymine. The calculated EFG tensors at the level of B3LYP and B3PW91 DFT methods and 6-311++G**and CC-pVTZ basis sets were converted to those experimentally measurable NQR parameters, quadrupole coupling constants and asymmetry parameters. The results reveal that because of strong contribution to N-H...O=C HBs, NQR parameters of O2, N1 and N3 undergo significant changes from monomer to the target molecule in cluster. Furthermore, the NQR parameters of O2 also undergo some changes because of non-classical C-H...O=C HBs.

  3. Interaction between anions and cationic metal complexes containing tridentate ligands with exo-C-H groups: complex stability and hydrogen bonding. (United States)

    Martínez-García, Héctor; Morales, Dolores; Pérez, Julio; Puerto, Marcos; del Río, Ignacio


    [Re(CO)3 ([9]aneS3 )][BAr'4 ] (1), prepared by reaction of ReBr(CO)5 , 1,4,7-trithiacyclononane ([9]aneS3 ) and NaBAr'4 , forms stable, soluble supramolecular adducts with chloride (2), bromide, methanosulfonate (3) and fluoride (4) anions. These new species were characterized by IR, NMR spectroscopy and, for 2 and 3, also by X-ray diffraction. The results of the solid state structure determinations indicate the formation of CH⋅⋅⋅X hydrogen bonds between the anion (X) and the exo-CH groups of the [9]aneS3 ligand, in accord with the relatively large shifts found by (1) H NMR spectroscopy in dichloromethane solution for those hydrogens. The stability of the chloride adduct contrasts with the lability of the [9]aneS3 ligand in allyldicarbonyl molybdenum complexes recently studied by us. With fluoride, in dichloromethane solution, a second, minor neutral dimeric species 5 is formed in addition to 4. In 4, the deprotonation of a CH group of the [9]aneS3 ligand, accompanied by CS bond cleavage and dimerization, afforded 5, featuring bridging thiolates. Compounds [Mo(η(3) -methallyl)(CO)2 (TpyN)][BAr'4 ] (6) and [Mo(η(3) -methallyl)(CO)2 (TpyCH)][BAr'4 ] (7) were synthesized by the reactions of [MoCl(η(3) -methallyl)(CO)2 (NCMe)2 ], NaBAr'4 and tris(2-pyridyl)amine (TpyN) or tris(2-pyridyl)methane (TpyCH) respectively, and characterized by IR and (1) H and (13) C NMR spectroscopy in solution, and by X-ray diffraction in the solid state. Compound 6 undergoes facile substitution of one of the 2-pyridyl groups by chloride, bromide, and methanosulfonate anions. Stable supramolecular adducts were formed between 7 and chloride, bromide, iodide, nitrate, and perrhenate anions. The solid state structures of these adducts (12-16) were determined by X-ray diffraction. Binding constants in dichloromethane were calculated from (1) H NMR titration data for all the new supramolecular adducts. The signal of the bridgehead CH group is the one that undergoes a

  4. Water as a green solvent for efficient synthesis of isocoumarins through microwave-accelerated and Rh/Cu-catalyzed C-H/O-H bond functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Li, Qiu; Yan, Yunnan; Wang, Xiaowei; Gong, Binwei; Tang, Xiaobo; Shi, JingJing; Xu, H. Eric; Yi, Wei [Shenyang; (Gannan); (Van Andel); (UST - China); (Chinese Aca. Sci.)


    Green chemistry that uses water as a solvent has recently received great attention in organic synthesis. Here we report an efficient synthesis of biologically important isocoumarins through direct cleavage of C–H/O–H bonds by microwave-accelerated and Rh/Cu-catalyzed oxidative annulation of various substituted benzoic acids, where water is used as the only solvent in the reactions. The remarkable features of this “green” methodology include high product yields, wide tolerance of various functional groups as substrates, and excellent region-/site-specificities, thus rendering this methodology a highly versatile and eco-friendly alternative to the existing methods for synthesizing isocoumarins and other biologically important derivatives such as isoquinolones.

  5. Resonating Valence Bond Quantum Monte Carlo: Application to the ozone molecule

    CERN Document Server

    Azadi, Sam; Kühne, Thomas D


    We study the potential energy surface of the ozone molecule by means of Quantum Monte Carlo simulations based on the resonating valence bond concept. The trial wave function consists of an antisymmetrized geminal power arranged in a single-determinant that is multiplied by a Jastrow correlation factor. Whereas the determinantal part incorporates static correlation effects, the augmented real-space correlation factor accounts for the dynamics electron correlation. The accuracy of this approach is demonstrated by computing the potential energy surface for the ozone molecule in three vibrational states: symmetric, asymmetric and scissoring. We find that the employed wave function provides a detailed description of rather strongly-correlated multi-reference systems, which is in quantitative agreement with experiment.

  6. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter


    -H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation...... an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence...

  7. Selective activation of C-F and C-H bonds with iron complexes, the relevant mechanism study by DFT calculations and study on the chemical properties of hydrido iron complex. (United States)

    Xu, Xiaofeng; Jia, Jiong; Sun, Hongjian; Liu, Yuxia; Xu, Wengang; Shi, Yujie; Zhang, Dongju; Li, Xiaoyan


    The reactions of (2,6-difluorophenyl)phenylmethanone (2,6-F(2)C(6)H(3)-C(=O)-C(6)H(5)) (1) and (2,6-difluorophenyl)phenylmethanimine (2,6-F(2)C(6)H(3)-C(=NH)-C(6)H(5)) (3) with Fe(PMe(3))(4) afforded different selective C-F/C-H bond activation products. The reaction of 1 with Fe(PMe(3))(4) gave rise to bis-chelate iron(II) complex [C(6)H(5)-C(=O)-3-FC(6)H(3))Fe(PMe(3))](2) (2) via C-F bond activation. The reaction of 3 with Fe(PMe(3))(4) delivered chelate hydrido iron(II) complex 2,6-F(2)C(6)H(3)-C(=NH)-C(6)H(4))Fe(H)(PMe(3))(3) (4) through C-H bond activation. The DFT calculations show the detailed elementary steps of the mechanism of formation of hydrido complex 4 and indicate 4 is the kinetically preferred product. Complex 4 reacted with HCl, CH(3)Br and CH(3)I delivered the chelate iron halides (2,6-F(2)C(6)H(3)-C(=NH)-C(6)H(4))Fe(PMe(3))(3)X (X = Cl (5); Br (6); I (7)). A ligand (PMe(3)) replacement by CO of 4 was observed giving (2,6-F(2)C(6)H(3)-C(=NH)-C(6)H(4))Fe(H)(CO)(PMe(3))(2) (8). The chelate ligand exchange occurred through the reaction of 4 with salicylaldehydes. The reaction of 4 with Me(3)SiC[triple bond, length as m-dash]CH afforded (2,6-F(2)C(6)H(3)-C([double bond, length as m-dash]N)-C(6)H(5))Fe(C≡C-SiMe(3))(PMe(3))(3) (11). A reaction mechanism from 4 to 11 was discussed with the support of IR monitoring. The molecular structures of complexes 2, 4, 6, 7, 10 and 11 were determined by X-ray diffraction.

  8. Recyclable and Reusable [RuCl2(p-cymene)]2/Cu(OAc)2/PEG-400/H2O System for Oxidative C-H Bond Alkenylations: Green Synthesis of Phthalides. (United States)

    Zhao, Hong; Zhang, Tinli; Yan, Tao; Cai, Mingzhong


    [RuCl2(p-cymene)]2 in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be an extremely efficient catalyst for the cross-dehydrogenative C-H bond alkenylation reaction between benzoic acids and alkenes. The reaction could be conducted at 80 °C using Cu(OAc)2·H2O as oxidant, yielding a variety of phthalide derivatives in good to excellent yields. More importantly, both [RuCl2(p-cymene)]2 and Cu(OAc)2 in the PEG-400/H2O system could be easily recycled and reused six times without any loss of catalytic activity.

  9. Reactivity of Tp(Me2) -supported yttrium alkyl complexes toward aromatic N-heterocycles: ring-opening or C-C bond formation directed by C-H activation. (United States)

    Yi, Weiyin; Zhang, Jie; Huang, Shujian; Weng, Linhong; Zhou, Xigeng


    Unusual chemical transformations such as three-component combination and ring-opening of N-heterocycles or formation of a carbon-carbon double bond through multiple C-H activation were observed in the reactions of Tp(Me2) -supported yttrium alkyl complexes with aromatic N-heterocycles. The scorpionate-anchored yttrium dialkyl complex [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with 1-methylimidazole in 1:2 molar ratio to give a rare hexanuclear 24-membered rare-earth metallomacrocyclic compound [Tp(Me2) Y(μ-N,C-Im)(η(2) -N,C-Im)]6 (1; Im=1-methylimidazolyl) through two kinds of C-H activations at the C2- and C5-positions of the imidazole ring. However, [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with two equivalents of 1-methylbenzimidazole to afford a C-C coupling/ring-opening/C-C coupling product [Tp(Me2) Y{η(3) -(N,N,N)-N(CH3 )C6 H4 NHCHC(Ph)CN(CH3 )C6 H4 NH}] (2). Further investigations indicated that [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with benzothiazole in 1:1 or 1:2 molar ratio to produce a C-C coupling/ring-opening product {(Tp(Me2) )Y[μ-η(2) :η(1) -SC6 H4 N(CHCHPh)](THF)}2 (3). Moreover, the mixed Tp(Me2) /Cp yttrium monoalkyl complex [(Tp(Me2) )CpYCH2 Ph(THF)] reacted with two equivalents of 1-methylimidazole in THF at room temperature to afford a trinuclear yttrium complex [Tp(Me2) CpY(μ-N,C-Im)]3 (5), whereas when the above reaction was carried out at 55 °C for two days, two structurally characterized metal complexes [Tp(Me2) Y(Im-Tp(Me2) )] (7; Im-Tp(Me2) =1-methyl-imidazolyl-Tp(Me2) ) and [Cp3 Y(HIm)] (8; HIm=1-methylimidazole) were obtained in 26 and 17 % isolated yields, respectively, accompanied by some unidentified materials. The formation of 7 reveals an uncommon example of construction of a CC bond through multiple C-H activations.

  10. Monte Carlo simulations on magnetic behavior of a spin-chain system in triangular lattice doped with antiferromagnetic bonds

    Institute of Scientific and Technical Information of China (English)

    YAO Xiao-yan; LI Peng-lei; DONG Shuai; LIU Jun-ming


    A three-dimensional Ising-like model doped with anti-ferromagnetic (AFM) bonds is proposed to investigate the magnetic properties of a doped triangular spin-chain system by using a Monte-Carlo simulation. The simulated results indicate that a steplike magnetization behavior is very sensitive to the concentration of AFM bonds. A low concentration of AFM bonds can suppress the stepwise behavior considerably, in accordance with doping experiments on Ca3Co206. The analysis of spin snapshots demonstrates that the AFM bond doping not only breaks the ferromagnetic ordered linear spin chains along the hexagonal c-axis but also has a great influence upon the spin configuration in the ab-plane.

  11. Gas-Phase Intercluster Thiyl-Radical Induced C-H Bond Homolysis Selectively Forms Sugar C2-Radical Cations of Methyl D-Glucopyranoside: Isotopic Labeling Studies and Cleavage Reactions (United States)

    Osburn, Sandra; Speciale, Gaetano; Williams, Spencer J.; O'Hair, Richard A. J.


    A suite of isotopologues of methyl D-glucopyranosides is used in conjunction with multistage mass spectrometry experiments to determine the radical site and cleavage reactions of sugar radical cations formed via a recently developed `bio-inspired' method. In the first stage of CID (MS2), collision-induced dissociation (CID) of a protonated noncovalent complex between the sugar and S-nitrosocysteamine, [H3NCH2CH2SNO + M]+, unleashes a thiyl radical via bond homolysis to give the noncovalent radical cation, [H3NCH2CH2S• + M]+. CID (MS3) of this radical cation complex results in dissociation of the noncovalent complex to generate the sugar radical cation. Replacement of all exchangeable OH and NH protons with deuterons reveals that the sugar radical cation is formed in a process involving abstraction of a hydrogen atom from a C-H bond of the sugar coupled with proton transfer to the sugar, to form [M - H• + D+]. Investigation of this process using individual C-D labeled sugars reveals that the main site of H/D abstraction is the C2 position, since only the C2-deuterium labeled sugar yields a dominant [M - D• + H+] product ion. The fragmentation reactions of the distonic sugar radical cation, [M - H•+ H+], were studied by another stage of CID (MS4). 13C-labeling studies revealed that a series of three related fragment ions each contain the C1-C3 atoms; these arise from cross-ring cleavage reactions of the sugar.

  12. Thermochemical properties of methyl-substituted cyclic alkyl ethers and radicals for oxiranes, oxetanes, and oxolanes: C-H bond dissociation enthalpy trends with ring size and ether site. (United States)

    Auzmendi-Murua, Itsaso; Charaya, Sumit; Bozzelli, Joseph W


    Cyclic ethers are an important product from the gas-phase reactions of hydrocarbon radicals with molecular oxygen in the atmospheric chemistry of diolefins and in low to moderate temperature combustion and oxidation reaction systems. They are also important in organic synthesis. Structures, and fundamental thermochemical parameters-enthalpy (ΔH°(f,298)), entropy (S°(298)), and heat capacity (C(p)(T))-have been calculated for a series of cyclic alkyl ethers and their carbon centered radicals. Enthalpies of formation (ΔH°(f,298)) are determined at the B3LYP/6-31G(d,p), B3LYP/6-31G(2d,2p), and CBS-QB3 levels using several work reactions for each species. Entropy (S) and heat capacity (C(p)(T)) values from vibration, translational, and external rotational contributions are calculated using the rigid-rotor-harmonic-oscillator approximation based on the vibration frequencies and structures obtained from the density functional studies. Contributions from the internal methyl rotors are substituted for torsion frequencies. Calculated enthalpies of formation for a series of 12 cyclic ethers and methyl substituted cyclic ethers are in good agreement with available literature values. C-H bond dissociation enthalpies are reported for 28 carbon sites of 3 to 5 member ring cyclic ethers for use in understanding effects of the ring and the ether oxygen on kinetics and stability. Trends in carbon-hydrogen bond energies for the ring and methyl substituents relative to ring size and to distance from the ether group are described.

  13. Aromatic C-H Bond Functionalization Induced by Electrochemically in Situ Generated Tris(p-bromophenyl)aminium Radical Cation: Cationic Chain Reactions of Electron-Rich Aromatics with Enamides. (United States)

    Li, Long-Ji; Jiang, Yang-Ye; Lam, Chiu Marco; Zeng, Cheng-Chu; Hu, Li-Ming; Little, R Daniel


    An effective Friedel-Crafts alkylation reaction of electron-rich aromatics with N-vinylamides, induced by electrochemically in situ-generated TBPA radical cation, has been developed; the resulting adducts are produced in good to excellent yields. In the "ex-cell" type electrolysis, TBPA is transformed to its oxidized form in situ and subsequently employed as an electron transfer reagent to initiate a cationic chain reaction. An easily recoverable and reusable polymeric ionic liquid-carbon black (PIL-CB) composite was also utilized as a supporting electrolyte for the electrochemical generation of TBPA cation radical, without sacrificing efficiency or stability after four electrolyses. Cyclic voltammetry analysis and the results of control experiments demonstrate that the reaction of electron-rich aromatics and N-vinylamides occurs via a cationic chain reaction, which takes place though an oxidative activation of a C-H bond of electron-rich aromatics instead of oxidation of the N-vinylamide as previously assumed.

  14. Enhanced Reactivity in Hydrogen Atom Transfer from Tertiary Sites of Cyclohexanes and Decalins via Strain Release: Equatorial C-H Activation vs Axial C-H Deactivation. (United States)

    Salamone, Michela; Ortega, Vanesa B; Bietti, Massimo


    Absolute rate constants for hydrogen atom transfer (HAT) from cycloalkanes and decalins to the cumyloxyl radical (CumO(•)) were measured by laser flash photolysis. Very similar reactivities were observed for the C-H bonds of cyclopentane and cyclohexane, while the tertiary C-H bond of methylcyclopentane was found to be 6 times more reactive than the tertiary axial C-H bond of methylcyclohexane, pointing toward a certain extent of tertiary axial C-H bond deactivation. Comparison between the cis and trans isomers of 1,2-dimethylcyclohexane, 1,4-dimethylcyclohexane and decalin provides a quantitative evaluation of the role played by strain release in these reactions. kH values for HAT from tertiary equatorial C-H bonds were found to be at least 1 order of magnitude higher than those for HAT from the corresponding tertiary axial C-H bonds (kH(eq)/kH(ax) = 10-14). The higher reactivity of tertiary equatorial C-H bonds was explained in terms of 1,3-diaxial strain release in the HAT transition state. Increase in torsional strain in the HAT transition state accounts instead for tertiary axial C-H bond deactivation. The results are compared with those obtained for the corresponding C-H functionalization reactions by dioxiranes and nonheme metal-oxo species indicating that CumO(•) can represent a convenient model for the reactivity patterns of these oxidants.

  15. Palladium Catalyzed Allylic C-H Alkylation: A Mechanistic Perspective

    Directory of Open Access Journals (Sweden)

    Casper Junker Engelin


    Full Text Available The atom-efficiency of one of the most widely used catalytic reactions for forging C-C bonds, the Tsuji-Trost reaction, is limited by the need of preoxidized reagents. This limitation can be overcome by utilization of the recently discovered palladium-catalyzed C-H activation, the allylic C-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation are highlighted with emphasis on those leading to C-C bond formation, but where it was deemed necessary for the general understanding of the process closely related C-H oxidations and aminations are also included. It is found that C-H cleavage is most likely achieved by ligand participation which could involve an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence of the benzoquinone/hydroquinone redox couple. Alternative methods for re-oxidation that does not rely on benzoquinone could be able to alleviate this limitation.

  16. Cobalt-Catalyzed Oxidative C-H/C-H Cross-Coupling between Two Heteroarenes. (United States)

    Tan, Guangying; He, Shuang; Huang, Xiaolei; Liao, Xingrong; Cheng, Yangyang; You, Jingsong


    The first example of cobalt-catalyzed oxidative C-H/C-H cross-coupling between two heteroarenes is reported, which exhibits a broad substrate scope and a high tolerance level for sensitive functional groups. When the amount of Co(OAc)2 ⋅4 H2 O is reduced from 6.0 to 0.5 mol %, an excellent yield is still obtained at an elevated temperature with a prolonged reaction time. The method can be extended to the reaction between an arene and a heteroarene. It is worth noting that the Ag2 CO3 oxidant is renewable. Preliminary mechanistic studies by radical trapping experiments, hydrogen/deuterium exchange experiments, kinetic isotope effect, electron paramagnetic resonance (EPR), and high resolution mass spectrometry (HRMS) suggest that a single electron transfer (SET) pathway is operative, which is distinctly different from the dual C-H bond activation pathway that the well-described oxidative C-H/C-H cross-coupling reactions between two heteroarenes typically undergo.

  17. Deriving molecular bonding from a macromolecular self-assembly using kinetic Monte Carlo simulations

    NARCIS (Netherlands)

    Silly, Fabien; Weber, Ulrich K.; Shaw, Adam Q.; Burlakov, Victor M.; Castell, Martin R.; Briggs, G. A. D.; Pettifor, David G.


    Macromolecules can form regular structures on inert surfaces, We have developed a combined empirical and modeling approach to derive the bonding. From experimental scanning tunneling microscopy images of structures formed on Au(111) by melamine, by 3,4,9, 10-perylene-tetracarboxylic-dianhydride, and

  18. Manganese Catalyzed C-H Halogenation. (United States)

    Liu, Wei; Groves, John T


    The remarkable aliphatic C-H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon-halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C-H bonds to C-Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L-Mn(V)═O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn-F fluorine source, effecting carbon-fluorine bond formation. Indeed, this idea

  19. Monte Carlos studies of critical and dynamic phenomena in mixed bond Ising model (United States)

    Santos-Filho, J. B.; Moreno, N. O.; de Albuquerque, Douglas F.


    The phase transition of a random mixed-bond Ising ferromagnet on a cubic lattice model is studied both numerically and analytically. In this work, we use the Metropolis and Wolff algorithm with histogram technique and finite size scaling theory to simulate the dynamics of the system. We obtained the thermodynamic quantities such as magnetization, susceptibility, and specific heat. Our results were compared with those obtained using a new technique in effective field theory that employs similar probability distribution within the framework of two-site clusters.

  20. Monte Carlo studies of the cubic lattice mixed-bond Ising model (United States)

    Santos-Filho, J. B.; Moreno, N. O.; de Albuquerque, D. F.; de Arruda, A. S.


    In this work, we used the Cluster Wolff algorithms to simulate the dynamics of the system. We obtained the thermodynamic quantities such as magnetization and susceptibility. Critical temperatures were estimated at the maximum of the susceptibility and with these values we made the phase diagram, TC versus p (the concentration of magnetic bonds) for different α values, being α the competition parameter. Our results were compared to those obtained by using a new technique in the effective field theory which employs similar probability distribution within the framework of two-site clusters.

  1. Free-Radical Triggered Ordered Domino Reaction: An Approach to C-C Bond Formation via Selective Functionalization of α-Hydroxyl-(sp(3))C-H in Fluorinated Alcohols. (United States)

    Xu, Zhengbao; Hang, Zhaojia; Liu, Zhong-Quan


    A free-radical mediated highly ordered radical addition/cyclization/(sp(3))C-C(sp(3)) formation domino reaction is developed. Three new C-C bonds are formed one by one in a mixed system. Furthermore, it represents the first example of cascade C-C bond formation via selective functionalization of α-hydroxyl-C(sp(3))-H in fluorinated alcohols.

  2. Vesicle structure and formation of AB/BC amphiphile mixture based on hydrogen bonding in a selective solvent: a Monte Carlo study. (United States)

    Han, Yuanyuan; Cui, Jie; Jiang, Wei


    The effect of hydrogen bonding (H-bonding) on vesicle structure and its formation of the mixture of AB/BC amphiphilic molecules in a selective solvent for A and C blocks were studied using Monte Carlo simulation. For the purpose of comparison, H-bonding and covalent bonding were introduced via the two ends of two B blocks. The simulation results indicate that associative interaction of H-bonding (ε(hb)) and repulsive interaction between A and C blocks (ε(AC)) are the two key factors that determine vesicle structure. Four typical vesicles--symmetric, three-layer asymmetric, microphase-separated, and Janus vesicles--can be obtained through the adjustment of ε(hb) and ε(AC). This result is interesting for experimental researchers for controlling vesicle structure and its properties through the introduction of H-bonding. More interestingly, the pathway of vesicle formation also depends on H-bonding. For an H-bonded system, the vesicle is more likely to be formed via diffusion of hydrophilic blocks into the center of spherical micelles. This process is independent of ε(AC). However, for a covalently bonded system, the vesicle is more likely to be formed via oblate membrane-closing for higher ε(AC). In addition, the vesicle is more likely to be formed via diffusion of hydrophilic blocks into the center of spherical micelles for lower ε(AC). Conformational investigation reveals that this H-bonding dependence results from the reversibility of H-bonding.

  3. Differential steric effects in Cl reactions with aligned CHD3(v1 = 1) by the R(0) and Q(1) transitions. I. Attacking the excited C-H bond (United States)

    Wang, Fengyan; Liu, Kopin


    When a CHD3 molecule is pumped to the C-H stretching-excited state by absorbing a linearly polarized infrared (IR) photon via the R(0) branch of the v1 = 1←0 transition, the rotational angular momentum j of the prepared state |" separators=" jK > = |" separators=" 10 > preferentially lies in a plane perpendicular to the IR polarization axis ɛIR. By way of contrast, when the Q(1) branch is used, the state of |" separators=" jK > = |" separators=" 1 ± 1 > is prepared with j aligned along the direction of ɛIR. Reported here is a detailed study of the title reaction by actively controlling the collision geometries under these two IR-excitation schemes at collision energy Ec = 8.6 kcal mol-1, using a crossed molecular beam, product imaging approach. We found that under the R(0) excitation, the polarization-dependent differential cross sections for the HCl(v = 0) + CD3(00) channel can largely be understood by invoking dual reaction mechanisms. The forward-scattered products are most likely mediated by a time-delayed resonance mechanism—as the formation of the HCl(v = 1) + CD3(00) channel, whereas the backward/sideways scattered products are governed by a direct abstraction mechanism. Compared to the previous results at lower Ec of 3.8 kcal mol-1, the sighting of opening-up the attack angle at the transition state of the direct pathway is proposed. Results under the Q(1) excitation are, however, perplexing and bear no obvious correlation to the corresponding ones for the R(0) excitation, defying simple intuitive interpretation. Possible reasons are put forward, which call for theoretical investigations for deeper insights. The results on the alternative isotope channel, DCl + CHD2, will be reported in the following paper.

  4. Diffusion Monte Carlo Study of Bond Dissociation Energies for BH2,B(OH)2, BCl2, and BCl

    Institute of Scientific and Technical Information of China (English)

    Hui-ran Li; Xin-lu Cheng; Hong Zhang


    On basis of bond dissociation energies (BDEs) for BH2,B(OH)2,BCl2,and BCl,the diffusion Monte Carlo (DMC) method is applied to explore the BDEs of HB-H,HOB-OH,ClB-Cl,and B-Cl.The effect of the choice of orbitals,as well as the backflow transformation,is studied.The Slater-Jastrow DMC algorithm gives BDEs of 359.1±0.12 kJ/mol for HB-H,410.5±0.50 kJ/mol for HOB-OH,357.8±1.46 kJ/mol for ClB-Cl,and 504.5±0.96 kJ/mol for B-Cl using B3PW91 orbitals and similar BDEs when B3LYP orbitals are used.DMC with backflow corrections (BF-DMC) gives a HB-H BDE of 369.9±0.12 kJ/mol which isclose to one of the available experimental value (375.8 kJ/mol).In the case of HOB-OH BDE,the BF-DMC calculation is 446.0±1.84 kJ/mol that is closer to the experimental BDE.The BF-DMC BDE for ClB-Cl is 343.2±2.34 kJ/mol and the BF-DMC B-Cl BDE is 523.3±0.33 kJ/mol,which are close to the experimental BDEs,341.9 and 530.0 kJ/mol,respectively.

  5. Formation and High Reactivity of the anti-Dioxo Form of High-Spin μ-Oxodioxodiiron(IV) as the Active Species That Cleaves Strong C-H Bonds. (United States)

    Kodera, Masahito; Ishiga, Shin; Tsuji, Tomokazu; Sakurai, Katsutoshi; Hitomi, Yutaka; Shiota, Yoshihito; Sajith, P K; Yoshizawa, Kazunari; Mieda, Kaoru; Ogura, Takashi


    Recently, it was shown that μ-oxo-μ-peroxodiiron(III) is converted to high-spin μ-oxodioxodiiron(IV) through O-O bond scission. Herein, the formation and high reactivity of the anti-dioxo form of high-spin μ-oxodioxodiiron(IV) as the active oxidant are demonstrated on the basis of resonance Raman and electronic-absorption spectral changes, detailed kinetic studies, DFT calculations, activation parameters, kinetic isotope effects (KIE), and catalytic oxidation of alkanes. Decay of μ-oxodioxodiiron(IV) was greatly accelerated on addition of substrate. The reactivity order of substrates is toluenecumenereaction with toluene/[D8 ]toluene is 95 at -30 °C, which the largest in diiron systems reported so far. The present diiron complex efficiently catalyzes the oxidation of various alkanes with H2 O2 .

  6. Main group multiple C-H/N-H bond activation of a diamine and isolation of a molecular dilithium zincate hydride: experimental and DFT evidence for alkali metal-zinc synergistic effects. (United States)

    Campbell, Ross; Cannon, Daniel; García-Álvarez, Pablo; Kennedy, Alan R; Mulvey, Robert E; Robertson, Stuart D; Sassmannshausen, Jörg; Tuttle, Tell


    The surprising transformation of the saturated diamine (iPr)NHCH(2)CH(2)NH(iPr) to the unsaturated diazaethene [(iPr)NCH═CHN(iPr)](2-) via the synergic mixture nBuM, (tBu)(2)Zn and TMEDA (where M = Li, Na; TMEDA = N,N,N',N'-tetramethylethylenediamine) has been investigated by multinuclear NMR spectroscopic studies and DFT calculations. Several pertinent intermediary and related compounds (TMEDA)Li[(iPr)NCH(2)CH(2)NH(iPr)]Zn(tBu)(2) (3), (TMEDA)Li[(iPr)NCH(2)CH(2)CH(2)N(iPr)]Zn(tBu) (5), {(THF)Li[(iPr)NCH(2)CH(2)N(iPr)]Zn(tBu)}(2) (6), and {(TMEDA)Na[(iPr)NCH(2)CH(2)N(iPr)]Zn(tBu)}(2) (11), characterized by single-crystal X-ray diffraction, are discussed in relation to their role in the formation of (TMEDA)M[(iPr)NCH═CHN(iPr)]Zn(tBu) (M = Li, 1; Na, 10). In addition, the dilithio zincate molecular hydride [(TMEDA)Li](2)[(iPr)NCH(2)CH(2)N(iPr)]Zn(tBu)H 7 has been synthesized from the reaction of (TMEDA)Li[(iPr)NCH(2)CH(2)NH(iPr)]Zn(tBu)(2)3 with nBuLi(TMEDA) and also characterized by both X-ray crystallographic and NMR spectroscopic studies. The retention of the Li-H bond of 7 in solution was confirmed by (7)Li-(1)H HSQC experiments. Also, the (7)Li NMR spectrum of 7 in C(6)D(6) solution allowed for the rare observation of a scalar (1)J(Li-H) coupling constant of 13.3 Hz. Possible mechanisms for the transformation from diamine to diazaethene, a process involving the formal breakage of four bonds, have been determined computationally using density functional theory. The dominant mechanism, starting from (TMEDA)Li[(iPr)NCH(2)CH(2)N(iPr)]Zn(tBu) (4), involves the formation of a hydride intermediate and leads directly to the observed diazaethene product. In addition the existence of 7 in equilibrium with 4 through the dynamic association and dissociation of a (TMEDA)LiH ligand, also provides a secondary mechanism for the formation of the diazaethene. The two reaction pathways (i.e., starting from 4 or 7) are quite distinct and provide excellent examples in which the

  7. Enantioselective, intermolecular benzylic C-H amination catalysed by an engineered iron-haem enzyme (United States)

    Prier, Christopher K.; Zhang, Ruijie K.; Buller, Andrew R.; Brinkmann-Chen, Sabine; Arnold, Frances H.


    C-H bonds are ubiquitous structural units of organic molecules. Although these bonds are generally considered to be chemically inert, the recent emergence of methods for C-H functionalization promises to transform the way synthetic chemistry is performed. The intermolecular amination of C-H bonds represents a particularly desirable and challenging transformation for which no efficient, highly selective, and renewable catalysts exist. Here we report the directed evolution of an iron-containing enzymatic catalyst—based on a cytochrome P450 monooxygenase—for the highly enantioselective intermolecular amination of benzylic C-H bonds. The biocatalyst is capable of up to 1,300 turnovers, exhibits excellent enantioselectivities, and provides access to valuable benzylic amines. Iron complexes are generally poor catalysts for C-H amination: in this catalyst, the enzyme's protein framework confers activity on an otherwise unreactive iron-haem cofactor.

  8. Scalable and sustainable electrochemical allylic C-H oxidation (United States)

    Horn, Evan J.; Rosen, Brandon R.; Chen, Yong; Tang, Jiaze; Chen, Ke; Eastgate, Martin D.; Baran, Phil S.


    New methods and strategies for the direct functionalization of C-H bonds are beginning to reshape the field of retrosynthetic analysis, affecting the synthesis of natural products, medicines and materials. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C-H functionalization, owing to the utility of enones and allylic alcohols as versatile intermediates, and their prevalence in natural and unnatural materials. Allylic oxidations have featured in hundreds of syntheses, including some natural product syntheses regarded as “classics”. Despite many attempts to improve the efficiency and practicality of this transformation, the majority of conditions still use highly toxic reagents (based around toxic elements such as chromium or selenium) or expensive catalysts (such as palladium or rhodium). These requirements are problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. This oxidation strategy is therefore rarely used for large-scale synthetic applications, limiting the adoption of this retrosynthetic strategy by industrial scientists. Here we describe an electrochemical C-H oxidation strategy that exhibits broad substrate scope, operational simplicity and high chemoselectivity. It uses inexpensive and readily available materials, and represents a scalable allylic C-H oxidation (demonstrated on 100 grams), enabling the adoption of this C-H oxidation strategy in large-scale industrial settings without substantial environmental impact.

  9. Superioridad relativa de los estimadores Kiviet y Blundell-Bond (GMM1 en paneles dinámicos. Un experimento Monte Carlo con muestras finitas

    Directory of Open Access Journals (Sweden)

    Andrés Eduardo Rangel Jiménez


    Full Text Available Dado el amplio uso de los datos de panel en modelos dinamicos, es relevante evaluar el desempeno de sus diferentes estimadores en muestras finitas en presencia de baja y alta persistencia. El presente articulo tiene como objetivo analizar, mediante simulaciones tipo Monte Carlo, las propiedades de los estimadores de efectos fijos (LSDV, Arellano y Bond (AB-GMM1, Blundell y Bond (BB-GMM1, Anderson y Hsiao (AH y Kiviet. Se concluye que en series no persistentes el estimador de Kiviet es el de mejor desempeno, basandose en los criterios de error cuadratico medio, sesgo y desviacion estandar; con alta persistencia, el estimador BB-GMM1 es el de mejor desempeno seguido por el estimador de Kiviet, que se comporta bien excepto en micropaneles con series persistentes.

  10. Superioridad relativa de los estimadores Kiviet y Blundell-Bond (GMM1 en paneles dinámicos. Un experimento Monte Carlo con muestras finitas

    Directory of Open Access Journals (Sweden)

    Andrés Eduardo Rangel Jiménez


    Full Text Available Dado el amplio uso de los datos de panel en modelos dinámicos, es relevante evaluar el desempeño de sus diferentes estimadores en muestras finitas en presencia de baja y alta persistencia. El presente artículo tiene como objetivo analizar, mediante simulaciones tipo Monte Carlo, las propiedades de los estimadores de efectos fijos (LSDV, Arellano y Bond (AB-GMM1, Blundell y Bond (BB-GMM1, Anderson y Hsiao (AH y Kiviet. Se concluye que en series no persistentes el estimador de Kiviet es el de mejor desempeño, basándose en los criterios de error cuadrático medio, sesgo y desviación estándar; con alta persistencia, el estimador BB-GMM1 es el de mejor desempeño seguido por el estimador de Kiviet, que se comporta bien excepto en micropaneles con series persistentes.

  11. Selective sp3 C-H alkylation via polarity-match-based cross-coupling (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.


    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp3)-C(sp2) coupling, there is a growing demand for C-H alkylation reactions, wherein sp3 C-H bonds are replaced with sp3 C-alkyl groups. Here we describe a polarity-match-based selective sp3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  12. 基于蒙特卡罗模拟的可转换债券定价研究%Monte Carlo-based pricing of convertible bonds

    Institute of Scientific and Technical Information of China (English)

    赵洋; 赵立臣


    The paper applied the least-square Monte Carlo method proposed by Longstaff,et price convertible bond,so as to solve the problem of prcing the path-dependent clauses and American option features embeded in convertible bonds.Convertible bonds are complex hybrid securities being subject to equity risk,credit risk,and interest rate risk.In the established pricing model,the assumption of constant volatility is relaxed and the volatility is estimated with GARCH (1,1),according to TF model,the credit risk is represented with the credit risk spread,and the yield curve is estimsted with Nelson-Siegel method.By empirical research,it is found that the convertible bonds in China are underpriced by 2% to 3%.%使用Longstaff等提出的最小二乘蒙特卡罗方法为可转换债券定价,从而解决为可转换债券中路径依赖条款和美式期权进行定价的难题.可转换债券是复杂的结构化产品,同时受股价风险、信用风险和利率风险影响.在建立的定价模型中,股价过程放松波动率为常数的假设,用GARCH(1,1)模型估计波动率,信用风险根据TF模型用常数信用利差代表,收益率曲线用Nelson-Siegel方法估计.通过实证检验发现国内可转换债券市场存在低估,低估幅度在2%~3%之间.

  13. Diffusion Monte Carlo applied to weak interactions - hydrogen bonding and aromatic stacking in (bio-)molecular model systems (United States)

    Fuchs, M.; Ireta, J.; Scheffler, M.; Filippi, C.


    Dispersion (Van der Waals) forces are important in many molecular phenomena such as self-assembly of molecular crystals or peptide folding. Calculating this nonlocal correlation effect requires accurate electronic structure methods. Usual density-functional theory with generalized gradient functionals (GGA-DFT) fails unless empirical corrections are added that still need extensive validation. Quantum chemical methods like MP2 and coupled cluster are more accurate, yet limited to rather small systems by their unfavorable computational scaling. Diffusion Monte Carlo (DMC) can provide accurate molecular total energies and remains feasible also for larger systems. Here we apply the fixed-node DMC method to (bio-)molecular model systems where dispersion forces are significant: (dimethyl-) formamide and benzene dimers, and adenine-thymine DNA base pairs. Our DMC binding energies agree well with data from coupled cluster (CCSD(T)), in particular for stacked geometries where GGA-DFT fails qualitatively and MP2 predicts too strong binding.

  14. Characterization of two alkyl hydroperoxide reductase C homologs alkyl hydroperoxide reductase C_H1 and alkyl hydroperoxide reductase C_H2 in Bacillus subtilis

    Institute of Scientific and Technical Information of China (English)

    Mee-Kyung; Cha; Yoo-Jeen; Bae; Kyu-Jeong; Kim; Byung-Joon; Park; Il-Han; Kim


    AIM: To identify alkyl hydroperoxide reductase subunit C(AhpC) homologs in Bacillus subtilis(B. subtilis) and to characterize their structural and biochemical properties. AhpC is responsible for the detoxification of reactive oxygen species in bacteria.METHODS: Two AhpC homologs(AhpC_H1 and AhpC_H2) were identified by searching the B. subtilis database; these were then cloned and expressed in Escherichia coli. AhpC mutants carrying substitutions of catalytically important Cys residues(C37S, C47 S, C166 S, C37/47 S, C37/166 S, C47/166 S, and C37/47/166 S for AhpC_H1; C52 S, C169 S, and C52/169 S for AhpC_H2) were obtained by site-directed mutagenesis and purified, and their structure-function relationship was analyzed. The B. subtilis ahp C genes were disrupted by the short flanking homology method, and the phenotypes of the resulting AhpC-deficient bacteria were examined.RESULTS: Comparative characterization of AhpC homologs indicates that AhpC_H1 contains an extra C37, which forms a disulfide bond with the peroxidatic C47, and behaves like an atypical 2-Cys AhpC, while AhpC_H2 functions like a typical 2-Cys AhpC. Tryptic digestion analysis demonstrated the presence of intramolecular Cys37-Cys47 linkage, which could be reduced by thioredoxin, resulting in the association of the dimer into higher-molecular-mass complexes. Peroxidase activity analysis of Cys→Ser mutants indicated that three Cys residues were involved in the catalysis. AhpC_H1 was resistant to inactivation by peroxide substrates, but had lower activity at physiological H2O2 concentrations compared to AhpC_H2, suggesting that in B. subtilis, the enzymes may be physiologically functional at different substrate concentrations. The exposure to organic peroxides induced AhpC_H1 expression, while AhpC_H1-deficient mutants exhibited growth retardation in the stationary phase, suggesting the role of AhpC_H1 as an antioxidant scavenger of lipid hydroperoxides and a stress-response factor in B. subtilis

  15. A study of H+H2 and several H-bonded molecules by phaseless auxiliary-field quantum Monte Carlo with plane wave and Gaussian basis sets. (United States)

    Al-Saidi, W A; Krakauer, Henry; Zhang, Shiwei


    The authors present phaseless auxiliary-field (AF) quantum Monte Carlo (QMC) calculations of the ground states of some hydrogen-bonded systems. These systems were selected to test and benchmark different aspects of the new phaseless AF QMC method. They include the transition state of H+H(2) near the equilibrium geometry and in the van der Walls limit, as well as the H(2)O, OH, and H(2)O(2) molecules. Most of these systems present significant challenges for traditional independent-particle electronic structure approaches, and many also have exact results available. The phaseless AF QMC method is used either with a plane wave basis with pseudopotentials or with all-electron Gaussian basis sets. For some systems, calculations are done with both to compare and characterize the performance of AF QMC under different basis sets and different Hubbard-Stratonovich decompositions. Excellent results are obtained using as input single Slater determinant wave functions taken from independent-particle calculations. Comparisons of the Gaussian based AF QMC results with exact full configuration interaction show that the errors from controlling the phase problem with the phaseless approximation are small. At the large basis-size limit, the AF QMC results using both types of basis sets are in good agreement with each other and with experimental values.

  16. Metal-Free sp(2)-C-H Borylation as a Common Reactivity Pattern of Frustrated 2-Aminophenylboranes. (United States)

    Chernichenko, Konstantin; Lindqvist, Markus; Kótai, Bianka; Nieger, Martin; Sorochkina, Kristina; Pápai, Imre; Repo, Timo


    C-H borylation is a powerful and atom-efficient method for converting affordable and abundant chemicals into versatile organic reagents used in the production of fine chemicals and functional materials. Herein we report a facile C-H borylation of aromatic and olefinic C-H bonds with 2-aminophenylboranes. Computational and experimental studies reveal that the metal-free C-H insertion proceeds via a frustrated Lewis pair mechanism involving heterolytic splitting of the C-H bond by cooperative action of the amine and boryl groups. The adapted geometry of the reactive B and N centers results in an unprecedentently low kinetic barrier for both insertion into the sp(2)-C-H bond and intramolecular protonation of the sp(2)-C-B bond in 2-ammoniophenyl(aryl)- or -(alkenyl)borates. This common reactivity pattern serves as a platform for various catalytic reactions such as C-H borylation and hydrogenation of alkynes. In particular, we demonstrate that simple 2-aminopyridinium salts efficiently catalyze the C-H borylation of hetarenes with catecholborane. This reaction is presumably mediated by a borenium species isoelectronic to 2-aminophenylboranes.

  17. Cp*Co(III)-Catalyzed Dehydrative C-H Allylation of 6-Arylpurines and Aromatic Amides Using Allyl Alcohols in Fluorinated Alcohols. (United States)

    Bunno, Youka; Murakami, Nanami; Suzuki, Yudai; Kanai, Motomu; Yoshino, Tatsuhiko; Matsunaga, Shigeki


    Cp*Co(III)-catalyzed C-H allylation of various aromatic C-H bonds using allyl alcohols as allylating reagents is described. Improved reaction conditions using fluorinated alcohol solvents afforded efficient directed C-H allylation of 6-arylpurines, benzamides, and a synthetically useful Weinreb amide with good functional group compatibility.

  18. Palladium-catalysed transannular C-H functionalization of alicyclic amines (United States)

    Topczewski, Joseph J.; Cabrera, Pablo J.; Saper, Noam I.; Sanford, Melanie S.


    Discovering pharmaceutical candidates is a resource-intensive enterprise that frequently requires the parallel synthesis of hundreds or even thousands of molecules. C-H bonds are present in almost all pharmaceutical agents. Consequently, the development of selective, rapid and efficient methods for converting these bonds into new chemical entities has the potential to streamline pharmaceutical development. Saturated nitrogen-containing heterocycles (alicyclic amines) feature prominently in pharmaceuticals, such as treatments for depression (paroxetine, amitifadine), diabetes (gliclazide), leukaemia (alvocidib), schizophrenia (risperidone, belaperidone), malaria (mefloquine) and nicotine addiction (cytisine, varenicline). However, existing methods for the C-H functionalization of saturated nitrogen heterocycles, particularly at sites remote to nitrogen, remain extremely limited. Here we report a transannular approach to selectively manipulate the C-H bonds of alicyclic amines at sites remote to nitrogen. Our reaction uses the boat conformation of the substrates to achieve palladium-catalysed amine-directed conversion of C-H bonds to C-C bonds on various alicyclic amine scaffolds. We demonstrate this approach by synthesizing new derivatives of several bioactive molecules, including varenicline.

  19. Charge-transfer-directed radical substitution enables para-selective C-H functionalization (United States)

    Boursalian, Gregory B.; Ham, Won Seok; Mazzotti, Anthony R.; Ritter, Tobias


    Efficient C-H functionalization requires selectivity for specific C-H bonds. Progress has been made for directed aromatic substitution reactions to achieve ortho and meta selectivity, but a general strategy for para-selective C-H functionalization has remained elusive. Herein we introduce a previously unappreciated concept that enables nearly complete para selectivity. We propose that radicals with high electron affinity elicit arene-to-radical charge transfer in the transition state of radical addition, which is the factor primarily responsible for high positional selectivity. We demonstrate with a simple theoretical tool that the selectivity is predictable and show the utility of the concept through a direct synthesis of aryl piperazines. Our results contradict the notion, widely held by organic chemists, that radical aromatic substitution reactions are inherently unselective. The concept of radical substitution directed by charge transfer could serve as the basis for the development of new, highly selective C-H functionalization reactions.

  20. Analyzing site selectivity in Rh2(esp)2-catalyzed intermolecular C-H amination reactions. (United States)

    Bess, Elizabeth N; DeLuca, Ryan J; Tindall, Daniel J; Oderinde, Martins S; Roizen, Jennifer L; Du Bois, J; Sigman, Matthew S


    Predicting site selectivity in C-H bond oxidation reactions involving heteroatom transfer is challenged by the small energetic differences between disparate bond types and the subtle interplay of steric and electronic effects that influence reactivity. Herein, the factors governing selective Rh2(esp)2-catalyzed C-H amination of isoamylbenzene derivatives are investigated, where modification to both the nitrogen source, a sulfamate ester, and substrate are shown to impact isomeric product ratios. Linear regression mathematical modeling is used to define a relationship that equates both IR stretching parameters and Hammett σ(+) values to the differential free energy of benzylic versus tertiary C-H amination. This model has informed the development of a novel sulfamate ester, which affords the highest benzylic-to-tertiary site selectivity (9.5:1) observed for this system.

  1. A steric tethering approach enables palladium-catalysed C-H activation of primary amino alcohols (United States)

    Calleja, Jonas; Pla, Daniel; Gorman, Timothy W.; Domingo, Victoriano; Haffemayer, Benjamin; Gaunt, Matthew J.


    Aliphatic primary amines are a class of chemical feedstock essential to the synthesis of higher-order nitrogen-containing molecules, commonly found in biologically active compounds and pharmaceutical agents. New methods for the construction of complex amines remain a continuous challenge to synthetic chemists. Here, we outline a general palladium-catalysed strategy for the functionalization of aliphatic C-H bonds within amino alcohols, an important class of small molecule. Central to this strategy is the temporary conversion of catalytically incompatible primary amino alcohols into hindered secondary amines that are capable of undergoing a sterically promoted palladium-catalysed C-H activation. Furthermore, a hydrogen bond between amine and catalyst intensifies interactions around the palladium and orients the aliphatic amine substituents in an ideal geometry for C-H activation. This catalytic method directly transforms simple, easily accessible amines into highly substituted, functionally concentrated and structurally diverse products, and can streamline the synthesis of biologically important amine-containing molecules.

  2. Visible light mediated efficient oxidative benzylic sp(3) C-H to ketone derivatives obtained under mild conditions using O2. (United States)

    Yi, Hong; Bian, Changliang; Hu, Xia; Niu, Linbin; Lei, Aiwen


    A photooxygenation of benzylic sp(3) C-H reaction has been demonstrated using O2 mediated by visible light. This protocol provides a simple and mild route to obtain ketones from benzylic sp(3) C-H bonds. Various benzylic sp(3) C-H bonds can be transformed into the desired ketone derivatives in moderate to good yields. The (18)O2 labelling experiments demonstrated that the oxygen introduced into ketone originated from dioxygen. A plausible mechanism has been proposed accordingly.

  3. Addition, cycloaddition, and metathesis reactions of the cationic carbyne complexes [Cp(CO)[sub 2]Mn[triple bond]CCH[sub 2]R][sup +] and neutral vinylidene complexes Cp(CO)[sub 2]M=C=C(H)R (M = Mn, Re)

    Energy Technology Data Exchange (ETDEWEB)

    Terry, M.R.; Mercando, L.A.; Kelley, C.; Geoffroy, G.L. (Pennsylvania State Univ., University Park, PA (United States)); Nombel, P.; Lugan, N.; Mathieu, R. (Laboratoire de Chimie de Coordination du CNRS, Toulouse (France)); Ostrander, R.L.; Owens-Waltermire, B.E.; Rheingold, A.L. (Univ. of Delaware, Newark, DE (United States))


    The cationic alkylidyne complexes [Cp(CO)[sub 2]M=VCCH[sub 2]R][sup +] (M = Re, R = H; M = Mn, R = H, Me, Ph) undergo facile deprotonation to give the corresponding neutral vinylidene complexes Cp(CO)[sub 2]M=C=C(H)R. For [Cp(CO)[sub 2]Re=VCCH[sub 3

  4. Overcoming the limitations of directed C-H functionalizations of heterocycles. (United States)

    Liu, Yue-Jin; Xu, Hui; Kong, Wei-Jun; Shang, Ming; Dai, Hui-Xiong; Yu, Jin-Quan


    In directed C-H activation reactions, any nitrogen or sulphur atoms present in heterocyclic substrates will coordinate strongly with metal catalysts. This coordination, which can lead to catalyst poisoning or C-H functionalization at an undesired position, limits the application of C-H activation reactions in heterocycle-based drug discovery, in which regard they have attracted much interest from pharmaceutical companies. Here we report a robust and synthetically useful method that overcomes the complications associated with performing C-H functionalization reactions on heterocycles. Our approach employs a simple N-methoxy amide group, which serves as both a directing group and an anionic ligand that promotes the in situ generation of the reactive PdX2 (X = ArCONOMe) species from a Pd(0) source using air as the sole oxidant. In this way, the PdX2 species is localized near the target C-H bond, avoiding interference from any nitrogen or sulphur atoms present in the heterocyclic substrates. This reaction overrides the conventional positional selectivity patterns observed with substrates containing strongly coordinating heteroatoms, including nitrogen, sulphur and phosphorus. Thus, this operationally simple aerobic reaction demonstrates that it is possible to bypass a fundamental limitation that has long plagued applications of directed C-H activation in medicinal chemistry.

  5. Spectroscopic Evidence for the Two C-H-Cleaving Intermediates of Aspergillus nidulans Isopenicillin N Synthase. (United States)

    Tamanaha, Esta; Zhang, Bo; Guo, Yisong; Chang, Wei-Chen; Barr, Eric W; Xing, Gang; St Clair, Jennifer; Ye, Shengfa; Neese, Frank; Bollinger, J Martin; Krebs, Carsten


    The enzyme isopenicillin N synthase (IPNS) installs the β-lactam and thiazolidine rings of the penicillin core into the linear tripeptide l-δ-aminoadipoyl-l-Cys-d-Val (ACV) on the pathways to a number of important antibacterial drugs. A classic set of enzymological and crystallographic studies by Baldwin and co-workers established that this overall four-electron oxidation occurs by a sequence of two oxidative cyclizations, with the β-lactam ring being installed first and the thiazolidine ring second. Each phase requires cleavage of an aliphatic C-H bond of the substrate: the pro-S-CCys,β-H bond for closure of the β-lactam ring, and the CVal,β-H bond for installation of the thiazolidine ring. IPNS uses a mononuclear non-heme-iron(II) cofactor and dioxygen as cosubstrate to cleave these C-H bonds and direct the ring closures. Despite the intense scrutiny to which the enzyme has been subjected, the identities of the oxidized iron intermediates that cleave the C-H bonds have been addressed only computationally; no experimental insight into their geometric or electronic structures has been reported. In this work, we have employed a combination of transient-state-kinetic and spectroscopic methods, together with the specifically deuterium-labeled substrates, A[d2-C]V and AC[d8-V], to identify both C-H-cleaving intermediates. The results show that they are high-spin Fe(III)-superoxo and high-spin Fe(IV)-oxo complexes, respectively, in agreement with published mechanistic proposals derived computationally from Baldwin's founding work.

  6. Mechanistic Insight into the Rh(III)-Catalyzed C-H Activation of 2-Acetyl-1-Arythydrazines in Water. (United States)

    Wu, Weirong; Liu, Tao; Huang, Caiyun; Zhang, Jing; Man, Xiaoping


    A mechanistic study of the Cp*Rh(III)-catalyzed C-H functionalization of 2-acetyl-1-arythydrazines with diazo compounds in water was carried out by using density functional theory calculations. The results reveal that the acetyl-bonded N-H deprotonation is prior to the phenyl C-H activation. The mechanisms from protonation by acetic acid disagree with the proposal by the Wang group. Different from the Rh(III)-catalyzed C-H activation reported by experimental literature, the rate-determining step of the whole catalytic cycle with an overall barrier of 31.7 kcal mol(-1) (IV → TS12-P') is the protonation process of hydroxy O rather than the C-H bond cleavage step. The present theoretical study rationalizes the experimental observation at the molecular level.

  7. Cp*Rh(III)-Catalyzed Low Temperature C-H Allylation of N-Aryl-trichloro Acetimidamide. (United States)

    Debbarma, Suvankar; Bera, Sourav Sekhar; Maji, Modhu Sudan


    The readily synthesized trichloro acetimidamide was found to be an excellent directing group for the directed C-H-allylation reactions. Depending on the allylating agent used, selectively either mono- or diallylated products were readily synthesized. Moreover, the trichloro acetimidamide directing group was found to be highly efficient even at lower temperature for the C-H-allylation reaction. Due to mildness of the reaction conditions, double bond isomerization or cyclization to indole side product was not observed.

  8. Ornstein-Uhlenbeck diffusion quantum Monte Carlo study on the bond lengths and harmonic frequencies of some first-row diatomic molecules (United States)

    Lu, Shih-I.


    This article accesses the performance of the Ornstein-Uhlenbeck diffusion quantum Monte Carlo with regard to the calculation of molecular geometries and harmonic frequencies of H2, LiH, HF, Li2, LiF, CO, N2, and F2 molecules. A comparison of the results for the eight first-row diatomic molecules from experiments, CCSD(T)/6-311G(3df,3pd) and CCSD(T)/cc-pV5Z levels of theory as well as our work is given. The results presented show that quantum Monte Carlo is becoming powerful tools for ab initio electronic structure calculations.

  9. Carbon dioxide utilization via carbonate-promoted C-H carboxylation (United States)

    Banerjee, Aanindeeta; Dick, Graham R.; Yoshino, Tatsuhiko; Kanan, Matthew W.


    Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO32-) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)—a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO32--promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.

  10. Carbon dioxide utilization via carbonate-promoted C-H carboxylation. (United States)

    Banerjee, Aanindeeta; Dick, Graham R; Yoshino, Tatsuhiko; Kanan, Matthew W


    Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO3(2-)) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)--a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO3(2-)-promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.

  11. Role of Lewis acid additives in a palladium catalyzed directed C-H functionalization reaction of benzohydroxamic acid to isoxazolone. (United States)

    Athira, C; Sunoj, Raghavan B


    Metallic salts as well as protic additives are widely employed in transition metal catalyzed C-H bond functionalization reactions to improve the efficiency of catalytic protocols. In one such example, ZnCl2 and pivalic acid are used as additives in a palladium catalyzed synthesis of isoxazolone from a readily available benzohydroxamic acid under one pot conditions. In this article, we present some important mechanistic insights into the role of ZnCl2 and pivalic acid, gained by using density functional theory (M06) computations. Two interesting modes of action of ZnCl2 are identified in various catalytic steps involved in the formation of isoxazolone. The conventional Lewis acid coordination wherein zinc chloride (ZnCl2·(DMA)) binds to the carbonyl group is found to be more favored in the C-H activation step. However, the participation of a hetero-bimetallic Pd-Zn species is preferred in reductive elimination leading to Caryl-N bond formation. Pivalic acid helps in relay proton transfer in C-H bond activation through a cyclometallation deprotonation (CMD) process. The explicit inclusion of ZnCl2 and solvent N,N-dimethyl acetamide (DMA) stabilizes the transition state and also helps reduce the activation barrier for the C-H bond activation step. The electronic communication between the two metal species is playing a crucial role in stabilizing the Caryl-N bond formation transition state through a Pd-Zn hetero-bimetallic interaction.

  12. Nanocomposite W-C : H diamond-like carbon coatings

    NARCIS (Netherlands)

    Strondl, Carl Gunnar Christian


    It has been demonstrated that the rotation speed of the substrate table and the gas flow rate of acetylene gas are important process parameters for determining the nano/micro-structure of W-C:H coatings. Either a homogeneous or a pronounced multilayer or a nanocomposite structure of the W-C:H

  13. Probing C-H⋯N interaction in acetylene-benzonitrile complex using matrix isolation infrared spectroscopy and DFT computations (United States)

    Gopi, R.; Ramanathan, N.; Sundararajan, K.


    Hydrogen-bonded complexes of acetylene (C2H2) and the benzonitrile (C6H5CN) have been investigated using matrix isolation infrared spectroscopy and DFT computations. The structure of the complexes and the energies were computed at B3LYP and B3LYP+D3 levels of theory using 6-311++G (d, p) and aug-cc-pVDZ basis sets. DFT computations indicated two minima corresponding to the C-H⋯N (global) and C-H⋯π interactions (local) of 1:1 C2H2-C6H5CN complexes, where C2H2 is the proton donor in both complexes. Experimentally, the 1:1 C-H⋯N complex identified from the shifts in the C-H and Ctbnd N stretching modes corresponding to the C2H2 and C6H5CN sub-molecules in N2 and Ar matrices. Atoms in Molecules and Natural Bond Orbital analyses were performed to understand the nature of interaction and to unravel the reasons for red-shifting of the C-H stretching frequency in these complexes. Energy decomposition analysis was carried out to discern the various stabilizing and destabilizing components as a result of hydrogen bonding in the C2H2-C6H5CN complexes.

  14. Enantioselective amine α-functionalization via palladium-catalysed C-H arylation of thioamides (United States)

    Jain, Pankaj; Verma, Pritha; Xia, Guoqin; Yu, Jin-Quan


    Saturated aza-heterocycles are highly privileged building blocks that are commonly encountered in bioactive compounds and approved therapeutic agents. These N-heterocycles are also incorporated as chiral auxiliaries and ligands in asymmetric synthesis. As such, the development of methods to functionalize the α-methylene C-H bonds of these systems enantioselectively is of great importance, especially in drug discovery. Currently, enantioselective lithiation with (-)-sparteine followed by Pd(0) catalysed cross-coupling to prepare α-arylated amines is largely limited to pyrrolidines. Here we report a Pd(II)-catalysed enantioselective α-C-H coupling of a wide range of amines, which include ethyl amines, azetidines, pyrrolidines, piperidines, azepanes, indolines and tetrahydroisoquinolines. Chiral phosphoric acids are demonstrated as effective anionic ligands for the enantioselective coupling of methylene C-H bonds with aryl boronic acids. This catalytic reaction not only affords high enantioselectivities, but also provides exclusive regioselectivity in the presence of two methylene groups in different steric environments.

  15. Oxidative esterification via photocatalytic C-H activation (United States)

    Direct oxidative esterification of alcohol via photocatalytic C-H activation has been developed using VO@g-C3N4 catalyst; an expeditious esterification of alcohols occurs under neutral conditions using visible light as the source of energy.

  16. C-H activation: Complex peptides made simple (United States)

    Bartlett, Sean; Spring, David R.


    Nature oxidizes biosynthetic intermediates into structurally and functionally diverse peptides. An iron-catalysed C-H oxidation mimics this approach in the lab, enabling chemists to synthesize structural analogues with ease.

  17. Probing the segmental mobility and energy of the active zones of a protein chain (aspartic acid protease) by a coarse-grained bond-fluctuation Monte Carlo simulation (United States)

    Pandey, Ras; Farmer, Barry


    A protein chain such as aspartic acid protease is described by a specific sequence of 99 residues each with its own specific characteristics. In a coarse-grained description, the backbone of a protein chain is described by nodes tethered together by peptide bonds where each node (the amino acid group) is characterized by molecular weight and hydrophobicity. A well-developed and somewhat mature computational modeling tool for the polymer chain such as the bond-fluctuation model is used to study such a specific protein chain with its constitutive amino groups and their sequence. The relative magnitude of hydrophobicity is used to develop appropriate interaction potentials for these amino acid groups in explicit solvent. The Metropolis algorithm is used to move each node and solvent constituent. Local energy and mobility of each amino group are analyzed along with global energy, mobility, and conformation of the protein chain. Effect of the solvent interaction and its concentration on these quantities will be presented.

  18. Spontaneous reduction and C-H borylation of arenes mediated by uranium(III) disproportionation (United States)

    Arnold, Polly L.; Mansell, Stephen M.; Maron, Laurent; McKay, David


    Transition-metal-arene complexes such as bis(benzene)chromium Cr(η6-C6H6)2 are historically important to d-orbital bonding theory and have modern importance in organic synthesis, catalysis and organic spintronics. In investigations of f-block chemistry, however, arenes are invariably used as solvents rather than ligands. Here, we show that simple uranium complexes UX3 (X = aryloxide, amide) spontaneously disproportionate, transferring an electron and X-ligand, allowing the resulting UX2 to bind and reduce arenes, forming inverse sandwich molecules [X2U(µ-η6:η6-arene)UX2] and a UX4 by-product. Calculations and kinetic studies suggest a ‘cooperative small-molecule activation’ mechanism involving spontaneous arene reduction as an X-ligand is transferred. These mild reaction conditions allow functionalized arenes such as arylsilanes to be incorporated. The bulky UX3 are also inert to reagents such as boranes that would react with the traditional harsh reaction conditions, allowing the development of a new in situ arene C-H bond functionalization methodology converting C-H to C-B bonds.

  19. Spontaneous reduction and C-H borylation of arenes mediated by uranium(III) disproportionation. (United States)

    Arnold, Polly L; Mansell, Stephen M; Maron, Laurent; McKay, David


    Transition-metal-arene complexes such as bis(benzene)chromium Cr(η(6)-C(6)H(6))(2) are historically important to d-orbital bonding theory and have modern importance in organic synthesis, catalysis and organic spintronics. In investigations of f-block chemistry, however, arenes are invariably used as solvents rather than ligands. Here, we show that simple uranium complexes UX(3) (X = aryloxide, amide) spontaneously disproportionate, transferring an electron and X-ligand, allowing the resulting UX(2) to bind and reduce arenes, forming inverse sandwich molecules [X(2)U(µ-η(6):η(6)-arene)UX(2)] and a UX(4) by-product. Calculations and kinetic studies suggest a 'cooperative small-molecule activation' mechanism involving spontaneous arene reduction as an X-ligand is transferred. These mild reaction conditions allow functionalized arenes such as arylsilanes to be incorporated. The bulky UX(3) are also inert to reagents such as boranes that would react with the traditional harsh reaction conditions, allowing the development of a new in situ arene C-H bond functionalization methodology converting C-H to C-B bonds.

  20. Quantum Monte Carlo Study of π-Bonded Transition Metal Organometallics: Neutral and Cationic Vanadium-Benzene and Cobalt-Benzene Half Sandwiches. (United States)

    Horváthová, L; Dubecký, M; Mitas, L; Štich, I


    We present accurate quantum Monte Carlo (QMC) calculations that enabled us to determine the structure, spin multiplicity, ionization energy, dissociation energy, and spin-dependent electronic gaps of neutral and positively charged vanadium-benzene and cobalt-benzene systems. From total/ionization energy, we deduce a sextet (quintet) state of neutral (cationic) vanadium-benzene systems and quartet (triplet) state of the neutral (cationic) cobalt-benzene systems. Vastly different energy gaps for the two spin channels are predicted for the vanadium-benzene system and broadly similar energy gaps for the cobalt-benzene system. For this purpose, we have used a multistage combination of techniques with consecutive elimination of systematic biases except for the fixed-node approximation in QMC. Our results significantly differ from the established picture based on previous less accurate calculations and point out the importance of high-level many-body methods for predictive calculations of similar transition metal-based organometallic systems.

  1. A Theoretical Study on Activation of C--H and C--Cl Bonds in CH3X (X=H,Cl) by Fe2+%Fe(2+)活化CH_3X(X=H,Cl)中C—H,C—Cl键的理论研究

    Institute of Scientific and Technical Information of China (English)

    孙小丽; 李吉来; 黄旭日; 孙家锺


    The reactions of Fe2+ with CH3X (X=H, Cl) have been studied by density functional theory method detailedly. The results demonstrated that the H abstraction in Eq. 4 can proceed via the lowest activation barrier (△Ga= 0.23 kcal/mol) in all feasible pathways. However, the mechanisms of oxidative insertion and the SN2 substitution are not competitive because of thermodynamic factors. The electronic structure analysis suggests that the overlap between metal 3d orbital and substrate σc x results in the preference of Fe2+ front side attack on the C--X bond. This study is expected to shed light on the nature of the title reac-tions and provide theoretical clues and foundation for future research.%采用密度泛函理论(DFT)详尽地研究了Fe2+与CH3X(X=H,Cl)的反应机理.结果表明在所有通道中,反应4的H提取能垒最低(Ga=0.23 kcal/mol),氧化插入机制和SN2取代机制没有竞争性.详尽的电子结构分析表明由于金属3d与底物的σ*C—X可以最好的重叠,从而Fe2+从前端进攻C—X键有利于反应.该研究揭示了其微观本质,为Fe2+活化C—X键等相关研究提供理论线索和依据.

  2. Mechanistic insights into C-H amination via dicopper nitrenes. (United States)

    Aguila, Mae Joanne B; Badiei, Yosra M; Warren, Timothy H


    We examine important reactivity pathways relevant to stoichiometric and catalytic C-H amination via isolable β-diketiminato dicopper alkylnitrene intermediates {[Cl2NN]Cu}2(μ-NR). Kinetic studies involving the stoichiometric amination of ethylbenzene by {[Cl2NN]Cu}2(μ-N(t)Bu) (3) demonstrate that the terminal nitrene [Cl2NN]Cu═N(t)Bu is the active intermediate in C-H amination. Initial rates exhibit saturation behavior at high ethylbenzene loadings and an inverse dependence on the copper species [Cl2NN]Cu, both consistent with dissociation of a [Cl2NN]Cu fragment from 3 prior to C-H amination. C-H amination experiments employing 1,4-dimethylcyclohexane and benzylic radical clock substrate support a stepwise H-atom abstraction/radical rebound pathway. Dicopper nitrenes [Cu]2(μ-NCHRR') derived from 1° and 2° alkylazides are unstable toward tautomerization to copper(I) imine complexes [Cu](HN═CRR'), rendering 1° and 2° alkylnitrene complexes unsuitable for C-H amination.

  3. The dimers of glyoxal and acrolein with H 2O and HF: Negative intramolecular coupling and blue-shifted C-H stretch (United States)

    Karpfen, Alfred; Kryachko, Eugene S.


    The structures and the vibrational spectra of the hydrogen-bonded complexes: glyoxal-H 2O, glyoxal-HF, acrolein-H 2O, and acrolein-HF, are investigated within the MP2/aug-cc-pVTZ computational approach. It is demonstrated that the calculated blue shifts of the C-H stretching frequencies in the glyoxal-H 2O complexes are only indirectly pertinent to hydrogen bonding to the C-H group. The comparison with the glyoxal-HF and the acrolein-HF complexes reveals that these blue shifts are a direct consequence of a negative intramolecular coupling between vicinal C dbnd O and C-H bonds in the aldehyde groups of isolated glyoxal and acrolein molecules. To support this interpretation, the halogen-bonded complexes glyoxal-BrF and acrolein-BrF are discussed.

  4. N-tosyloxycarbamates as a source of metal nitrenes: rhodium-catalyzed C-H insertion and aziridination reactions. (United States)

    Lebel, Hélène; Huard, Kim; Lectard, Sylvain


    The rhodium-catalyzed decomposition of N-tosyloxycarbamates to generate metal nitrenes which undergo intramolecular C-H insertion or aziridination reaction is described. Aliphatic N-tosyloxycarbamates produce oxazolidinones with high yields and stereospecificity through insertion in benzylic, tertiary, and secondary C-H bonds. Intramolecular aziridination occurs with allylic N-tosyloxycarbamates to produce aziridines as single diastereomers. The reaction proceeds at room temperature using a rhodium catalyst and an excess of potassium carbonate and does not require the use of strong oxidant, such as hypervalent iodine reagents. A rhodium nitrene species is presumably involved, as both reactions are stereospecific.

  5. Properties of a-C:H:Si thin films deposited by middle-frequency magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Jinlong, E-mail: [State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, Lanzhou University of Technology, Lanzhou 730050 (China); School of Science, Lanzhou University of Technology, Lanzhou 730050 (China); Wang, Yubao; Du, Jinfang; Yang, Hua [State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, Lanzhou University of Technology, Lanzhou 730050 (China); Hao, Junying, E-mail: [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)


    Highlights: • The a-C:H:Si films were deposited by magnetron sputtering Si target in argon and methane gas mixture atmosphere. • The growth of a-C:H:Si films is classified into three modes with increasing of methane flow rate. • The a-C:H:Si films at moderate methane flow rate exhibit low stress, high hardness and superior tribological properties. - Abstract: The silicon doped hydrogenated amorphous carbon (a-C:H:Si) films were prepared on silicon substrates by middle-frequency magnetron sputtering silicon target in an argon and methane gas mixture atmosphere. The deposition rate, chemical composition, structure, surface properties, stress, hardness and tribological properties in the ambient air of the films were systemically investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscopy (AFM), nanoindentation and tribological tester. The results show that doped silicon content in the films is controlled in the wide range from 39.7 at.% to 0.2 at.% by various methane gas flow rate, and methane flow rate affects not only the silicon content but also its chemical bonding structure in the films due to the transformation of sputtering modes. Meanwhile, the sp{sup 3} carbon component in the films linearly increases with increasing of methane flow rate. The film deposited at moderate methane flow rate of 40–60 sccm exhibits the very smooth surface (RMS roughness 0.4 nm), low stress (0.42 GPa), high hardness (21.1 GPa), as well as low friction coefficient (0.038) and wear rate (1.6 × 10{sup −7} mm{sup 3}/Nm). The superior tribological performance of the films could be attributed to the formation and integral covering of the transfer materials on the sliding surface and their high hardness.

  6. Conformation of a coarse-grained protein chain (an aspartic acid protease) model in effective solvent by a bond-fluctuating Monte Carlo simulation (United States)

    Pandey, R. B.; Farmer, B. L.


    In a coarse-grained description of a protein chain, all of the 20 amino acid residues can be broadly divided into three groups: Hydrophobic (H) , polar (P) , and electrostatic (E) . A protein can be described by nodes tethered in a chain with a node representing an amino acid group. Aspartic acid protease consists of 99 residues in a well-defined sequence of H , P , and E nodes tethered together by fluctuating bonds. The protein chain is placed on a cubic lattice where empty lattice sites constitute an effective solvent medium. The amino groups (nodes) interact with the solvent (S) sites with appropriate attractive (PS) and repulsive (HS) interactions with the solvent and execute their stochastic movement with the Metropolis algorithm. Variations of the root mean square displacements of the center of mass and that of its center node of the protease chain and its gyration radius with the time steps are examined for different solvent strength. The structure of the protease swells on increasing the solvent interaction strength which tends to enhance the relaxation time to reach the diffusive behavior of the chain. Equilibrium radius of gyration increases linearly on increasing the solvent strength: A slow rate of increase in weak solvent regime is followed by a faster swelling in stronger solvent. Variation of the gyration radius with the time steps suggests that the protein chain moves via contraction and expansion in a somewhat quasiperiodic pattern particularly in strong solvent.

  7. Deposition and characterisation of multilayer hard coatings. Ti/TiN{delta}/TiC{sub x}N{sub y}/(TiC) a-C:H/(Ti) a-C:H

    Energy Technology Data Exchange (ETDEWEB)

    Burinprakhon, T


    Multilayer hard coatings containing Ti, TiN{delta}, TiC{sub x}N{sub y}, (TiC{sub m}) a-C:H, (TiC{sub n}) a-C:H, and (Ti) a-C:H were deposited on commercially pure titanium substrates by using an asymmetric bipolar pulsed-dc reactive magnetron sputtering of a titanium target, with Ar, Ar+N{sub 2}, Ar+N{sub 2}+CH{sub 4}, and Ar+CH{sub 4} gas mixtures. The microstructures, elemental compositions and bonding states of the interlayers and the coating surfaces were studied by using cross-sectional transmission electron microscopy (XTEM), electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The microstructure development of the multilayer coating was strongly influenced by target poisoning. As a result of the complete poisoning of the titanium target during the deposition of TiN{delta} and TiC{sub x}N{sub y} interlayers, the a-C:H interlayers containing graded titanium and nitrogen contents were found to develop successively to the TiC{sub x}N{sub y} interlayer without the formation of near-stoichiometric TiC. The (TiC{sub m}) a-C:H interlayer consisted of nano-particles of distorted fcc crystal structure embedded in the a-C:H matrix. The (TiC{sub n}) a-C:H and (Ti) a-C:H top layers were found to be a-C:H matrix without nano-particles. In the (Ti) a-C:H top layer there was no measurable amount of Ti observed, regardless of the variation of CH{sub 4} concentration between 37.5 and 60 % flow rate in Ar+-CH4 gas mixture. The top layer (Ti) a-C:H was found to contain approximately 10 atomic % nitrogen, due to N{sub 2} contamination during deposition caused by low conductance of N{sub 2} through the nominally closed valve of the mass flow controller. The change of the CH{sub 4} concentration during deposition of the top layer (Ti) a-C:H, however, showed a strong influence on the hydrogen content. The comparison of the fluorescence background of the Raman spectra revealed that hydrogen-less (Ti) a-C:H

  8. Deposition of a-C:H films on inner surface of high-aspect-ratio microchannel (United States)

    Hirata, Yuki; Choi, Junho


    Hydrogenated amorphous carbon (a-C:H) films were prepared on inner surface of 100-μm-width microchannel by using a bipolar-type plasma based ion implantation and deposition. The microchannel was fabricated using a silicon plate, and two kinds of microchannels were prepared, namely, with a bottom layer (open at one end) and without a bottom layer (open at both ends). The distribution of thickness and hardness of films was evaluated by SEM and nanoindentation measurements, respectively, and the microstructures of films were evaluated by Raman spectroscopy. Furthermore, the behavior of ions and radicals was analyzed simultaneously by combining the calculation methods of Particle-In-Cell/Monte Carlo Collision and Direct Simulation Monte Carlo to investigate the coating mechanism for the microchannel. It was found that the film thickness decreased as the depth of the coating position increased in the microchannels where it is open at one end. The uniformity of the film thickness improved by increasing the negative pulse voltage because ions can arrive at the deeper part of the microchannel. In addition, the hardness increased as the depth of the coating position increased. This is because the radicals do not arrive at the deeper part of the microchannel, and the incident proportion of ions relative to that of radicals increases, resulting in a high hardness due to the amorphization of the film. The opening area of the microchannel where the aspect ratio is very small, radicals dominate the incident flux, whereas ions prevail over radicals above an aspect ratio of about 7.5. On the other hand, in the microchannels that are open at both ends, there were great improvements in uniformity of the film thickness, hardness, and the film structure. The a-C:H films were successfully deposited on the entire inner surface of a microchannel with an aspect ratio of 20.

  9. Computational study on C-H...π interactions of acetylene with benzene, 1,3,5-trifluorobenzene and coronene. (United States)

    Dinadayalane, Tandabany C; Paytakov, Guvanchmyrat; Leszczynski, Jerzy


    Meta-hybrid density functional theory calculations using M06-2X/6-31+G(d,p) and M06-2X/6-311+G(d,p) levels of theory have been performed to understand the strength of C-H(…)π interactions of two possible types for benzene-acetylene, 1,3,5-trifluorobenzene-acetylene and coronene-acetylene complexes. Our study reveals that the C-H(...)π interaction complex where acetylene located above to the center of benzene ring (classical T-shaped) is the lowest energy structure. This structure is twice more stable than the configuration characterized by H atom of benzene interacting with the π-cloud of acetylene. The binding energy of 2.91 kcal/mol calculated at the M06-2X/6-311+G(d,p) level for the lowest energy configuration (1A) is in very good agreement with the experimental binding energy of 2.7 ± 0.2 kcal/mol for benzene-acetylene complex. Interestingly, the C-H(...)π interaction of acetylene above to the center of the aromatic ring is not the lowest energy configuration for 1,3,5-trifluorobenzene-acetylene and coronene-acetylene complexes. The lowest energy configuration (2A) for the former complex possesses both C-H(...)π interaction and C-H(...)F hydrogen bond, while the lowest energy structure for the coronene-acetylene complex involves both π-π and C-H(...)π interactions. C-H stretching vibrational frequencies and the frequency shifts are reported and analyzed for all of the configurations. We observed red-shift of the vibrational frequency for the stretching mode of the C-H bond that interacts with the π-cloud. Acetylene in the lowest-energy structures of the complexes exhibits significant red-shift of the C-H stretching frequency and change in intensity of the corresponding vibrational frequency, compared to bare acetylene. We have examined the molecular electrostatic potential on the surfaces of benzene, 1,3,5-trifluorobenzene, coronene and acetylene to explain the binding strengths of various complexes studied here.

  10. High growth rate of a-SiC:H films using ethane carbon source by HW-CVD method

    Indian Academy of Sciences (India)

    Mahesh M Kamble; Vaishali S Waman; Sanjay S Ghosh; Azam Mayabadi; Vasant G Sathe; T Shripathi; Habib M Pathan; Sandesh R Jadkar


    Hydrogenated amorphous silicon carbide (a-SiC:H) thin films were prepared using pure silane (SiH4) and ethane (C2H6), a novel carbon source, without hydrogen dilution using hot wire chemical vapour deposition (HW-CVD) method at low substrate temperature (200 °C) and at reasonably higher deposition rate (19.5 Å/s < d < 35.2 Å/s). Formation of a-SiC:H films has been confirmed from FTIR, Raman and XPS analysis. Influence of deposition pressure on compositional, structural, optical and electrical properties has been investigated. FTIR spectroscopy analysis revealed that there is decrease in C–H and Si–H bond densities while, Si–C bond density increases with increase in deposition pressure. Total hydrogen content drops from 22.6 to 14.4 at.% when deposition pressure is increased. Raman spectra show increase in structural disorder with increase in deposition pressure. It also confirms the formation of nearly stoichiometric a-SiC:H films. Bandgap calculated using both Tauc’s formulation and absorption at 104 cm-1 shows decreasing trend with increase in deposition pressure. Decrease in refractive index and increase in Urbach energy suggests increase in structural disorder and microvoid density in the films. Finally, it has been concluded that C2H6 can be used as an effective carbon source in HW-CVD method to prepare stoichiometric a-SiC:H films.

  11. Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand. (United States)

    Shang, Rui; Ilies, Laurean; Nakamura, Eiichi


    Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.

  12. Enantioselective Intramolecular Hydroarylation of Alkenes via Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Harada, Hitoshi; Thalji, Reema; Bergman, Robert; Ellman, Jonathan


    Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe){sub 2}]{sub 2} and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer.

  13. Eco-friendly solvents for palladium-catalyzed desulfitative C-H bond arylation of heteroarenes. (United States)

    Hfaiedh, Anoir; Yuan, Kedong; Ben Ammar, Hamed; Ben Hassine, Bechir; Soulé, Jean-François; Doucet, Henri


    Herein, we report the Pd-catalyzed regioselective direct arylation of heteroarenes in which benzenesulfonyl chlorides are used as coupling partners through a desulfitative cross-coupling that can be performed in diethyl carbonate (DEC) or cyclopentyl methyl ether (CPME) as green and renewable solvents or even in neat conditions instead of dioxane or dimethylacetamide (DMA). Under these solvent conditions, the reaction proceeds with a wide range of heteroarenes. C2- or C5-arylated products were obtained with furan and pyrrole derivatives. Benzofuran was also arylated regioselectively at the C2-position, whereas the reaction proceeds selectively at the C3- or C4-positions if thiophenes and benzothiophenes are used. Moreover, in some cases, especially with 1-methylindole, solvent-free conditions afforded better regioselectivities and/or yields than the reaction performed in the presence of solvents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Ruthenium-catalyzed C-H/N-O bond functionalization: green isoquinolone syntheses in water. (United States)

    Ackermann, Lutz; Fenner, Sabine


    Ruthenium-catalyzed isoquinolone syntheses with ample scope were accomplished through carboxylate assistance in environmentally benign water as a reaction medium. The high chemoselectivity of the ruthenium(II) carboxylate complex also set the stage for the direct use of free hydroxamic acids for annulations of alkynes.

  15. Enantioselective Intramolecular Hydroarylation of Alkenes via Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Harada, Hitoshi; Thalji, Reema; Bergman, Robert; Ellman, Jonathan


    Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe){sub 2}]{sub 2} and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer.

  16. Rh(III)-Catalyzed Diastereoselective Annulation of Amides with Quinone Monoacetals: Access to Bridged Nine-Membered Heterocycles via C-H Activation. (United States)

    Yang, Wei; Dong, Jinhuan; Wang, Jingyi; Xu, Xianxiu


    An unprecedented Rh(III)-catalyzed annulation of various benzamides and acrylamides with quinone monoacetals was developed for the facile and efficient one-pot synthesis of bridged nine-membered benzo[c]azonine-1,5(2H)-diones and 2-azabicyclo[4.3.1]dec-4-ene-3,8-diones. It is the first example of synthesis of nine-membered heterocycles through Rh(III)-catalyzed C-H bond functionalization, and both aryl and vinyl C-H bonds are tolerant in this reaction. A plausible mechanism is proposed on the basis of control experiments.

  17. Electron energy-loss spectroscopy analysis of low-temperature plasma-enhanced chemically vapor deposited a-C:H films

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A.J.; Benson, D.K.; Tracy, C.E.; Kazmerski, L.L.; Wager, J.F.


    Electron energy-loss spectroscopy (EELS) has been applied to the analysis of a-C:H films grown on various substrates by a unique low-temperature (<100 /sup 0/C) plasma-enhanced chemical vapor deposition (PECVD) process using ethylene and hydrogen gases. EELS data are used to characterize the relative amounts of fourfold coordinated sp/sup 3/ carbon bonding to threefold coordinated sp/sup 2/ carbon bonding as well as the relative order/disorder due to substrate effects. Ellipsometric and transmission measurements provide optical constants for the PECVD a-C:H films.

  18. A potential role of substrate as a base for deprotonation pathway in Rh-catalysed C-H amination of heteroArenes: DFT insights

    KAUST Repository

    Ajitha, Manjaly John


    The possibility of direct introduction of a new functionality through C–H bond activation is an attractive strategy in covalent synthesis. Here, we investigated the mechanism of Rh-catalysed C-H amination of the hetero-aryl substrate (2-phenylpyridine) using phenyl azide as nitrogen source by density functional theory (DFT). For the deprotocyclometallation and protodecyclometallation processes of the title reaction, we propose a stepwise base-assisted mechanism (pathway I) instead of previously reported concerted mechanism (pathway II). In the new mechanism proposed here, 2-phenylpyridine acts as a base in the initial deprotonation step (C-H bond cleavage) and transports the proton towards the final protonation step. In fact, the N-H bond of the strong conjugate acid (formed during initial C-H bond cleavage) considered in pathway I (via TS4) is more acidic than the C-H bond of the neutral substrate considered in pathway II (via TS5). The higher activation barrier of TS5 mainly originates from the ring strain of the four membered cyclic transition state. The vital role of base, as disclosed here, can potentially have broader mechanistic implications for the development of reaction conditions of transition metal catalysed reactions.

  19. Microstructure of a-C:H films prepared on a microtrench and analysis of ions and radicals behavior

    Energy Technology Data Exchange (ETDEWEB)

    Hirata, Yuki; Choi, Junho, E-mail: [Department of Mechanical Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)


    Amorphous carbon films (a-C:H) were prepared on a microtrench (4-μm pitch and 4-μm depth), and the uniformity of film thickness and microstructure of the films on the top, sidewall, and bottom surfaces of the microtrench were evaluated by scanning electron microscopy and Raman spectroscopy. The a-C:H films were prepared by bipolar-type plasma based ion implantation and deposition (bipolar PBII&D), and the negative pulse voltage, which is the main parameter dominating the film structure, was changed from −1.0 to −15 kV. Moreover, the behavior of ions and radicals was analyzed simultaneously by combining the calculation methods of Particle-In-Cell/Monte Carlo Collision (PIC-MCC) and Direct Simulation Monte Carlo (DSMC) to investigate the coating mechanism for the microtrench. The results reveal that the thickness uniformity of a-C:H films improves with decreasing negative pulse voltage due to the decreasing inertia of incoming ions from the trench mouth, although the film thickness on the sidewall tends to be much smaller than that on the top and bottom surfaces of the trench. The normalized flux and the film thickness show similar behavior, i.e., the normalized flux or thickness at the bottom surface increases at low negative pulse voltages and then saturates at a certain value, whereas at the sidewall it monotonically decreases with increasing negative voltage. The microstructure of a-C:H films on the sidewall surface is very different from that on the top and bottom surfaces. The film structure at a low negative pulse voltage shifts to more of a polymer-like carbon (PLC) structure due to the lower incident energy of ions. Although the radical flux on the sidewall increases slightly, the overall film structure is not significantly changed because this film formation at a low negative voltage is originally dominated by radicals. On the other hand, the flux of radicals is dominant on the sidewall in the case of high negative pulse voltage, resulting in a

  20. Hydrocarbon plume discrimination using the C-H stretch region of the Infrared spectrum using OP-FTIR. (United States)

    Crampton, R. S.; Pikelnaya, O.; Polidori, A.; Tisopulos, L.; Perry, S.


    Open path FTIR spectroscopy can measure many different gases including most gaseous hydrocarbons in the atmosphere. Individual Hydrocarbons can be identified in the fingerprint region (500 cm-1 to 1500 cm-1) due to unique bond absorption features. Often times the strongest absorption is not unique because it is a result of the C-H bonds stretching. These bonds and absorption features are in all hydrocarbons and overlap (2850 cm-1 to 3000 cm-1) so they are not ideal for identification of individual compounds. For this reason any FTIR investigations treat total hydrocarbons as hexane or pentane equivalent. This way the C-H stretch can be used to get real information about the total hydrocarbons when the individual compounds cannot be quantified. In the fall of 2015, KASSAY Field Services, Inc, participated in a program sponsored by the South Coast Air Quality Management District (SCAQMD) to conduct open path FTIR measurements downwind of oil wells located in the southern California basin. Most of the oil wells for this measurement study reside in the town of Signal Hill, CA. In a location such as Signal Hill (part of Long Beach, CA) there are always some Hydrocarbons in the air due to vehicles, gas stations, the oil and gas industry, and other sources mixed together. Each source has a different combination of hydrocarbons resulting in different shapes of absorption in the C-H stretch region. The final shape is a result of the ratio of all the absorber concentrations multiplied by the I.R. features of each. We investigated how the C-H stretch absorption feature shape changes over time and space in a complicated air shed and what the implications for possible source apportionment without needing highly accurate quantification of many gases.

  1. C-H activation of ethers by pyridine tethered PCsp3P-type iridium complexes. (United States)

    Cui, Peng; Babbini, Dominic C; Iluc, Vlad M


    Iridium PCsp3P complexes featuring a novel bis(2-diphenylphosphinophenyl)-2-pyridylmethane ligand (PC(Py)HP) are reported. C-H activation reactions between the dihydride complex [(PC(Py)P)Ir(H)2] and tetrahydrofuran or methyl tert-butyl ether in the presence of a hydrogen acceptor, norbornene (NBE), at ambient temperature led exclusively to the hydrido oxyalkyl complexes, [(PC(Py)P)IrH(C4H7O)] and [(PC(Py)P)IrH(CH2O(t)Bu)], respectively. The internal pyridine donor is important and stabilizes these species by coordination to the iridium center. The coordination of pyridine to the iridium center is labile, however, and its dissociation occurs in the presence of a suitable substrate, as demonstrated by the intramolecular nucleophilic attack of pyridine on a vinylidene intermediate generated from PhC[triple bond, length as m-dash]CH.

  2. Site-selective C-H arylation of primary aliphatic amines enabled by a catalytic transient directing group (United States)

    Liu, Yongbing; Ge, Haibo


    Transition-metal-catalysed direct C-H bond functionalization of aliphatic amines is of great importance in organic and medicinal chemistry research. Several methods have been developed for the direct sp3 C-H functionalization of secondary and tertiary aliphatic amines, but site-selective functionalization of primary aliphatic amines in remote positions remains a challenge. Here, we report the direct, highly site-selective γ-arylation of primary alkylamines via a palladium-catalysed C-H bond functionalization process on unactivated sp3 carbons. Using glyoxylic acid as an inexpensive, catalytic and transient directing group, a wide array of γ-arylated primary alkylamines were prepared without any protection or deprotection steps. This approach provides straightforward access to important structural motifs in organic and medicinal chemistry without the need for pre-functionalized substrates or stoichiometric directing groups and is demonstrated here in the synthesis of analogues of the immunomodulatory drug fingolimod directly from commercially available 2-amino-2-propylpropane-1,3-diol.

  3. Catalytic C-H imidation of aromatic cores of functional molecules: ligand-accelerated Cu catalysis and application to materials- and biology-oriented aromatics. (United States)

    Kawakami, Takahiro; Murakami, Kei; Itami, Kenichiro


    Versatile imidation of aromatic C-H bonds was accomplished. In the presence of copper bromide and 6,6'-dimethyl-2,2'-bipyridyl, a range of aromatics, such as polycyclic aromatic hydrocarbons, aromatic bowls, porphyrins, heteroaromatics, and natural products, can be imidated by N-fluorobenzenesulfonimide. A dramatic ligand-accelerated copper catalysis and an interesting kinetic profile were uncovered.

  4. Synthesis of 1H-indazoles and 1H-pyrazoles via FeBr3/O2 mediated intramolecular C-H amination. (United States)

    Zhang, Tianshui; Bao, Weiliang


    A new synthesis of substituted 1H-indazoles and 1H-pyrazoles from arylhydrazones via FeBr(3)/O(2) mediated C-H activation/C-N bond formation reactions is reported. The corresponding 1,3-diaryl-substituted indazoles and trisubstituted pyrazoles were obtained in moderate to excellent yields under mild conditions.

  5. Fundamental reactivity of the Metal-Carbon bond in cyclometalated PNC-complexes

    NARCIS (Netherlands)

    Jongbloed, L.S.


    The activation of C-H bonds by transition metals and the reactivity of the corresponding metal-carbon bond are interesting research topics form different point of views. Catalytic C-H bond functionalization has emerged as a highly active research area for the development of green construction of Car

  6. Fundamental reactivity of the Metal-Carbon bond in cyclometalated PNC-complexes

    NARCIS (Netherlands)

    L.S. Jongbloed


    The activation of C-H bonds by transition metals and the reactivity of the corresponding metal-carbon bond are interesting research topics form different point of views. Catalytic C-H bond functionalization has emerged as a highly active research area for the development of green construction of Car

  7. Aerobic Linear Allylic C-H Amination: Overcoming Benzoquinone Inhibition. (United States)

    Pattillo, Christopher C; Strambeanu, Iulia I; Calleja, Pilar; Vermeulen, Nicolaas A; Mizuno, Tomokazu; White, M Christina


    An efficient aerobic linear allylic C-H amination reaction is reported under palladium(II)/bis-sulfoxide/Brønsted base catalysis. The reaction operates under preparative, operationally simple conditions (1 equiv of olefin, 1 atm O2 or air) with reduced Pd(II)/bis-sulfoxide catalyst loadings while providing higher turnovers and product yields than systems employing stoichiometric benzoquinone (BQ) as the terminal oxidant. Pd(II)/BQ π-acidic interactions have been invoked in various catalytic processes and are often considered beneficial in promoting reductive functionalizations. When such electrophilic activation for functionalization is not needed, however, BQ at high concentrations may compete with crucial ligand (bis-sulfoxide) binding and inhibit catalysis. Kinetic studies reveal an inverse relationship between the reaction rate and the concentration of BQ, suggesting that BQ is acting as a ligand for Pd(II) which results in an inhibitory effect on catalysis.

  8. Two-State Reactivity in Low-Valent Iron-Mediated C-H Activation and the Implications for Other First-Row Transition Metals. (United States)

    Sun, Yihua; Tang, Hao; Chen, Kejuan; Hu, Lianrui; Yao, Jiannian; Shaik, Sason; Chen, Hui


    C-H bond activation/functionalization promoted by low-valent iron complexes has recently emerged as a promising approach for the utilization of earth-abundant first-row transition metals to carry out this difficult transformation. Herein we use extensive density functional theory and high-level ab initio coupled cluster calculations to shed light on the mechanism of these intriguing reactions. Our key mechanistic discovery for C-H arylation reactions reveals a two-state reactivity (TSR) scenario in which the low-spin Fe(II) singlet state, which is initially an excited state, crosses over the high-spin ground state and promotes C-H bond cleavage. Subsequently, aryl transmetalation occurs, followed by oxidation of Fe(II) to Fe(III) in a single-electron transfer (SET) step in which dichloroalkane serves as an oxidant, thus promoting the final C-C coupling and finalizing the C-H functionalization. Regeneration of the Fe(II) catalyst for the next round of C-H activation involves SET oxidation of the Fe(I) species generated after the C-C bond coupling. The ligand sphere of iron is found to play a crucial role in the TSR mechanism by stabilization of the reactive low-spin state that mediates the C-H activation. This is the first time that the successful TSR concept conceived for high-valent iron chemistry is shown to successfully rationalize the reactivity for a reaction promoted by low-valent iron complexes. A comparative study involving other divalent middle and late first-row transition metals implicates iron as the optimum metal in this TSR mechanism for C-H activation. It is predicted that stabilization of low-spin Mn(II) using an appropriate ligand sphere should produce another promising candidate for efficient C-H bond activation. This new TSR scenario therefore emerges as a new strategy for using low-valent first-row transition metals for C-H activation reactions.

  9. C-H complex in Si observed at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Hoffmann, L.; Lavrov, E.V.; Bech Nielsen, B. [Aarhus Univ. (Denmark). Inst. for Fysik og Astronomi


    Local vibrational modes of a carbon-hydrogen complex have been identified with infrared absorption spectroscopy. After implantation of protons or deuterons at {approx}20 K a carbon mode at 596 cm{sup -1} and a hydrogen mode at 1884 cm{sup -1} are observed in the sample annealed at 180 K. The two modes originate from the same defect, which is tentatively identified as bond centred hydrogen in the vicinity of a nearby substitutional carbon atom. (orig.) 10 refs.

  10. Cu(II) catalyzed imine C-H functionalization leading to synthesis of 2,5-substituted 1,3,4-oxadiazoles. (United States)

    Guin, Srimanta; Ghosh, Tuhin; Rout, Saroj Kumar; Banerjee, Arghya; Patel, Bhisma K


    A direct access to symmetrical and unsymmetrical 2,5-disubstituted [1,3,4]-oxadiazoles has been accomplished through an imine C-H functionalization of N-arylidenearoylhydrazide using a catalytic quantity of Cu(OTf)(2). This is the first example of amidic oxygen functioning as a nucleophile in a Cu-catalyzed oxidative coupling of an imine C-H bond. These reactions can be performed in air atmosphere and moisture making it exceptionally practical for application in organic synthesis.

  11. Incorporated W Roles on Microstructure and Properties of W-C:H Films by a Hybrid Linear Ion Beam Systems

    Directory of Open Access Journals (Sweden)

    Peng Guo


    Full Text Available W-incorporated diamond-like carbon (W-C:H films were fabricated by a hybrid beams system consisting of a DC magnetron sputtering and a linear ion source. The W concentration (1.08~31.74 at.% in the film was controlled by varying the sputtering current. The cross-sectional topography, composition, and microstructure of the W-C:H films were investigated by SEM, XPS, TEM, and Raman spectroscopy. The mechanical and tribological properties of the films as a function of W concentration were evaluated by a stress-tester, nanoindentation, and ball-on-disk tribometer, respectively. The results showed that films mainly exhibited the feature of amorphous carbon when W concentration of the films was less than 4.38 at.%, where the incorporated W atoms would be bonded with C atoms and resulted in the formation of WC1-x nanoparticles. The W-C:H film with 4.38 at.% W concentration showed a minimum value of residual compressive stress, a higher hardness, and better tribological properties. Beyond this W concentration range, both the residual stress and mechanical properties were deteriorated due to the growth of tungsten carbide nanoparticles in the carbon matrix.

  12. Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen, E-mail: [Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid (Spain)


    The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader’s quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN ({sup 1}Σ) and hydrideisocyanidezinc HZnNC ({sup 1}Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn]{sup +} composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn{sup +} ({sup 2}Σ) and HCNZn{sup +} ({sup 2}Σ)

  13. Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study. (United States)

    Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen


    The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader's quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN ((1)Σ) and hydrideisocyanidezinc HZnNC ((1)Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn](+) composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn(+) ((2)Σ) and HCNZn(+) ((2)Σ).

  14. Unexpected red shift of C-H vibrational band of Methyl benzoate

    CERN Document Server

    Maiti, Kiran Sankar; Scheurer, Christoph


    The C-H vibrational bands become more and more important in the structural determination of biological molecules with the development of CARS microscopy and 2DIR spectroscopy. Due to the congested pattern, near degeneracy, and strong anharmonicity of the C-H stretch vibrations, assignment of the C-H vibrational bands are often misleading. Anharmonic vibrational spectra calculation with multidimensional potential energy surface interprets the C-H vibrational spectra more accurately. In this article we have presented the importance of multidimensional potential energy surface in anharmonic vibrational spectra calculation and discuss the unexpected red shift of C-H vibrational band of Methyl benzoate.

  15. Proposal of an Amide-Directed Carbocupration Mechanism for Copper-Catalyzed meta-Selective C-H Arylation of Acetanilides by Diaryliodonium Salts

    Institute of Scientific and Technical Information of China (English)

    Song-lin Zhang; Yu-qiang Ding


    We examined the puzzling mechanism for Cu-catalyzed meta-C-H arylation reaction of anilides by diaryliodonium salts through systematic theoretical analysis.The previously proposed anti-oxy-cupration mechanism featuring anti- 1,2- or anti- 1,4-addition of cuprate and oxygen to the phenyl ring generating a meta-cuprated intermediate was excluded due to the large activation barriers.Alternatively,a new amide-directed carbocupration mechanism was proposed which involves a critical rate- and regio-determining step of amide-directed addition of the Cu(III)-aryl bond across the phenyl C2=C3 double bond to form an orthocuprated,meta-arylated intermediate.This mechanism is kinetically the most favored among several possible mechanisms such as ortho- or para-cupration/migration mechanism,direct meta C-H bond cleavage mediated by Cu(III) or Cu(I),and Cu(III)-catalyzed ortho-directed C-H bond activation mechanism.Furthermore,the predicted regioselectivity based on this mechanism has been shown to favor the meta-arylation that is consistent with the experimental observations.

  16. Hydrogen atom transfer from 1,n-alkanediamines to the cumyloxyl radical. Modulating C-H deactivation through acid-base interactions and solvent effects. (United States)

    Milan, Michela; Salamone, Michela; Bietti, Massimo


    A time-resolved kinetic study on the effect of trifluoroacetic acid (TFA) on the hydrogen atom transfer (HAT) reactions from 1,n-alkanediamines (R2N(CH2)nNR2, R = H, CH3; n = 1-4), piperazine, and 1,4-dimethylpiperazine to the cumyloxyl radical (CumO(•)), has been carried out in MeCN and DMSO. Very strong deactivation of the α-C-H bonds has been observed following nitrogen protonation and the results obtained have been explained in terms of substrate basicity, of the distance between the two basic centers and of the solvent hydrogen bond acceptor ability. At [substrate] ≤ 1/2 [TFA] the substrates exist in the doubly protonated form HR2N(+)(CH2)nN(+)R2H, and no reaction with CumO(•) is observed. At 1/2 [TFA] [TFA], HAT occurs from the α-C-H bonds of R2N(CH2)nNR2, and the mesured kH values are very close to those obtained in the absence of TFA. Comparison between MeCN and DMSO clearly shows that in the monoprotonated diamines R2N(CH2)nN(+)R2H remote C-H deactivation can be modulated through solvent hydrogen bonding.

  17. Aging of oxygen and hydrogen plasma discharge treated a-C:H and ta-C coatings

    Energy Technology Data Exchange (ETDEWEB)

    Bachmann, Svenja [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); BMW Group, Hufelandstraße 4, 80788 Munich (Germany); Schulze, Marcus [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); Morasch, Jan [Institute of Materials Science, Technische Universität Darmstadt, Surface Science Division, Jovanka-Bonschits-Straße 2, 64287 Darmstadt (Germany); Hesse, Sabine [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); Hussein, Laith [Eduard-Zintl-Institut, Department of Chemistry, Technische Universität Darmstadt, Alarich-Weiss-Str. 12, 64287, Darmstadt (Germany); Krell, Lisa; Schnagl, Johann [BMW Group, Hufelandstraße 4, 80788 Munich (Germany); Stark, Robert W. [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); and others


    Highlights: • The water CA of O{sub 2} and H{sub 2} plasma treated a-C:H and ta-C changes from hydrophillic to hydrophobic on aging. • XPS study indicates that the decrease in surface energy of plasma treated a-C:H and ta-C could be due to adsorption of organic component from air. • The COFLFM of O{sub 2} and H{sub 2} plasma treated a-C:H and ta-C decreased upon aging. • The COF of glycerol lubricated ta-C showed no sign of change upon aging. - Abstract: Surface modification with gas plasma is an efficient and easy way to improve the surface energy and the tribological behavior of diamond-like carbon (DLC) coatings, e.g., in biomedical implants or as protective coatings. However, the long-term performance of the plasma treated DLC coatings is not fully clear. We thus studied the long-term stability of two kinds of DLC coatings, namely (a) hydrogenated amorphous carbon (a-C:H) and (b) tetrahedral amorphous carbon (ta-C) treated at different radio frequency (RF) power and time of oxygen (O{sub 2}) and hydrogen (H{sub 2}) plasma. Their surface properties, e.g. surface wettability, structure and tribological behavior, were studied at regular intervals for a period of two months using contact angle goniometer, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), lateral force microscopy (LFM) and ball on disc apparatus. The surface energy of both the coatings decreased upon aging. The higher the RF power and time of treatment, the higher was the hydrophobicity upon aging. XPS analysis showed that the increase in hydrophobicity could be due to adsorption of unavoidable volatile organic components in the atmosphere. The H{sub 2} plasma treated ta-C was capable of rearranging its structural bonds upon aging. The nano-friction measurements by LFM showed that the coefficient of friction of plasma treated a-C:H and ta-C decreased upon aging. The results indicate that the surface properties of plasma treated a‐C:H and ta‐C are not stable on long-term and are

  18. Hydrogen Bonding to Alkanes: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen; Olesen, Solveig Gaarn


    The structural, vibrational, and energetic properties of adducts of alkanes and strong cationic proton donors were studied with composite ab initio calculations. Hydrogen bonding in [D-H+ H-alkyl] adducts contributes to a significant degree to the interactions between the two components, which...... is substantiated by NBO and AIM results. The hydrogen bonds manifest themselves in the same manner as conventional hydrogen bonds, D-H bond elongation, D-H vibrational stretching frequency red shift and intensity increase, and adduct stabilization. The alkane adducts also exhibit elongation of the C-H bonds...

  19. Impacts of hydrogen dilution on growth and optical properties of a-SiC:H films

    Institute of Scientific and Technical Information of China (English)

    HU Zhihua; LIAO Xianbo; DIAO Hongwei; KONG Guanglin; ZENG Xiangbo; XU Yanyue


    Hydrogenated amorphous silicon-carbon (a-SiC:H) films were deposited by plasma enhanced chemical vapor deposition (PECVD) with a fixed methane to silane ratio ([CH4]/[SiH4]) of 1.2 and a wide range of hydrogen dilution (RH=[H2]/[SiH4 + CH4]) values of 12, 22, 33, 102 and 135. The impacts of RH on the structural and optical properties of the films were investigated by using UV-VIS transmission, Fourier transform infrared (FTIR) absorption, Raman scattering and photoluminescence (PL) measur- ements. The effects of high temperature annealing on the films were also probed. It is found that with increasing hydrogen dilution, the optical band gap increases, and the PL peak blueshifts from ~1.43 to 1.62 Ev. In annealed state, the room temperature PL peak for the low RH samples disappears, while the PL peak for the high RH samples appears at ~2.08 Ev, which is attributed to nanocrystalline Si particles confined by Si-C and Si-O bonds.

  20. Spectroscopic Study of Plasma Polymerized a-C:H Films Deposited by a Dielectric Barrier Discharge

    Directory of Open Access Journals (Sweden)

    Thejaswini Halethimmanahally Chandrashekaraiah


    Full Text Available Plasma polymerized a-C:H thin films have been deposited on Si (100 and aluminum coated glass substrates by a dielectric barrier discharge (DBD operated at medium pressure using C2Hm/Ar (m = 2, 4, 6 gas mixtures. The deposited films were characterized by Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS, Raman spectroscopy, and ellipsometry. FT-IRRAS revealed the presence of sp3 and sp2 C–H stretching and C–H bending vibrations of bonds in the films. The presence of D and G bands was confirmed by Raman spectroscopy. Thin films obtained from C2H4/Ar and C2H6/Ar gas mixtures have ID/IG ratios of 0.45 and 0.3, respectively. The refractive indices were 2.8 and 3.1 for C2H4/Ar and C2H6/Ar films, respectively, at a photon energy of 2 eV.

  1. Computational rationalization of the selective C-H and C-F activations of fluoroaromatic imines and ketones by cobalt complexes. (United States)

    Li, Jingjing; Zhang, Dongju; Sun, Hongjian; Li, Xiaoyan


    While selective C-H and C-F activations of fluoroaromatic imines and ketones with transition metal complexes supported by PMe3 have been successfully achieved in recent publications, insight into the molecular mechanism and energetics of those reactions is still lacking. Focusing on three typical substrates, 2,6-difluorobenzophenone imine (A) and 2,6-difluorobenzophenone (B), and 2,4'-difluorobenzophenone (C), the present work theoretically studied their C-H and C-F cyclometalation reactions promoted by the activator Co(PMe3)4 or CoMe(PMe3)4. It is found that reaction A + Co(PMe3)4 favors the C-F activation, reaction A + CoMe(PMe3)4 prefers the C-H activation, whereas both the C-H and C-F activation pathways may be viable for reactions B + CoMe(PMe3)4 and C + CoMe(PMe3)4. The experimentally observed C-H and C-F cyclometalation products have been rationalized by analyzing the thermodynamic and kinetic properties of two activation pathways. From calculated results combined with the experimental observations, we believe that three factors, i.e. the oxidation state of the metal center in the activators, the anchoring group of substrates, and substituted fluoroatom counts of the aromatic ring in substrates, affect the selectivity of C-H and C-F activations of fluoroaromatic ketones and imines. Calculated results are enlightening about the rational design of activators and substrates of fluoroaromatic imines and ketones to obtain the exclusive C-H or C-F bond activation product.

  2. The I{sub c}(H)-T{sub c}(H) phase boundary of superconducting Nb thin films with periodic and quasiperiodic antidot arrays

    Energy Technology Data Exchange (ETDEWEB)

    Bothner, D.; Kemmler, M.; Cozma, R.; Kleiner, R.; Koelle, D. [Physikalisches Institut and Center for Collective Quantum Phenomena, Universitaet Tuebingen (Germany); Misko, V.; Peeters, F. [Departement Fysica, Universiteit Antwerpen (Belgium); Nori, F. [Advanced Science Institute, RIKEN (Japan)


    The magnetic field dependent critical current I{sub c}(H) of superconducting thin films with artificial defects strongly depends on the symmetry of the defect arrangement. Likewise the critical temperature T{sub c}(H) of superconducting wire networks is heavily influenced by the symmetry of the system. Here we present experimental data on the I{sub c}(H)-T{sub c}(H) phase boundary of Nb thin films with artificial defect lattices of different symmetries. For this purpose we fabricated 60 nm thick Nb films with antidots in periodic (triangular) and five different quasiperiodic arrangements. The parameters of the antidot arrays were varied to investigate the influence of antidot diameter and array density. Experiments were performed with high temperature stability ({delta}T<1 mK) at 0.5{<=}T/T{sub c}{<=}1. From the I-V-characteristics at variable H and T we extract I{sub c}(H) and T{sub c}(H) for different voltage and resistance criteria. The experimental data for the critical current density are compared with results from numerical molecular dynamics simulations.

  3. Hydrogen bonds in PC61BM solids (United States)

    Sheng, Chun-Qi; Li, Wen-Jie; Du, Ying-Ying; Chen, Guang-Hua; Chen, Zheng; Li, Hai-Yang; Li, Hong-Nian


    We have studied the hydrogen bonds in PC61BM solids. Inter-molecular interaction is analyzed theoretically for the well-defined monoclinic (P21/n) structure. The results indicate that PC61BM combines into C-H⋯Od bonded molecular chains, where Od denotes the doubly-bonded O atom of PC61BM. The molecular chains are linked together by C-H⋯Os bonds, where Os denotes the singly-bonded O atom of PC61BM. To reveal the consequences of hydrogen bond formation on the structural properties of PC61BM solids (not limited to the monoclinic structure), we design and perform some experiments for annealed samples with the monoclinic (P21/n) PC61BM as starting material. The experiments include differential scanning calorimetry, X-ray diffraction and infrared absorption measurements. Structural phase transitions are observed below the melting point. The C-H⋯Od bonds seem persisting in the altered structures. The inter-molecular hydrogen bonds can help to understand the phase separation in polymer/PC61BM blends and may be responsible for the existence of liquid PC61BM.

  4. Room temperature copper(II)-catalyzed oxidative cyclization of enamides to 2,5-disubstituted oxazoles via vinylic C-H functionalization. (United States)

    Cheung, Chi Wai; Buchwald, Stephen L


    A copper(II)-catalyzed oxidative cyclization of enamides to oxazoles via vinylic C-H bond functionalization at room temperature is described. Various 2,5-disubstituted oxazoles bearing aryl, vinyl, alkyl, and heteroaryl substituents could be synthesized in moderate to high yields. This reaction protocol is complementary to our previously reported iodine-mediated cyclization of enamides to afford 2,4,5-trisubstituted oxazoles.

  5. Synthesis of 2,3-dihydro-1H-indazoles by Rh(III)-catalyzed C-H cleavage of arylhydrazines. (United States)

    Yao, Jinzhong; Feng, Ruokun; Lin, Cong; Liu, Zhanxiang; Zhang, Yuhong


    A rhodium-catalyzed efficient method for the synthesis of 2,3-dihydro-1H-indazoles is described. The reaction of arylhydrazines with olefins results in the corresponding 2,3-dihydro 1H-indazoles with exclusive regioselectivity via C-H bond activation. The utility of the methodology is illustrated by a rapid synthesis of 1H-indazoles under mild reaction conditions in half an hour.

  6. Distortion/interaction analysis reveals the origins of selectivities in iridium-catalyzed C-H borylation of substituted arenes and 5-membered heterocycles


    Green, AG; Liu, P.; Merlic, CA; Houk, KN


    The iridium-catalyzed borylation of mono- and disubstituted arenes and heteroarenes has been studied with density functional theory. The distortion/interaction model was employed to understand the origins of selectivities in these reactions. Computations revealed that the transition states for C-H oxidative addition are very late, resembling the aryl iridium hydride intermediate with a fully formed Ir-C bond. Consequently, the regioselectivity is mainly controlled by differences in the intera...

  7. Rh(III)-Catalyzed meta-C-H Olefination Directed by a Nitrile Template. (United States)

    Xu, Hua-Jin; Lu, Yi; Farmer, Marcus E; Wang, Huai-Wei; Zhao, Dan; Kang, Yan-Shang; Sun, Wei-Yin; Yu, Jin-Quan


    A range of Rh(III)-catalyzed ortho-C-H functionalizations have been developed; however, extension of this reactivity to remote C-H functionalizations through large-ring rhodacyclic intermediates has yet to be demonstrated. Herein we report the first example of the use of a U-shaped nitrile template to direct Rh(III)-catalyzed remote meta-C-H activation via a postulated 12-membered macrocyclic intermediate. Because the ligands used for Rh(III) catalysts are significantly different from those of Pd(II) catalysts, this offers new opportunities for future development of ligand-promoted meta-C-H activation reactions.

  8. Extended Ensemble Monte Carlo


    Iba, Yukito


    ``Extended Ensemble Monte Carlo''is a generic term that indicates a set of algorithms which are now popular in a variety of fields in physics and statistical information processing. Exchange Monte Carlo (Metropolis-Coupled Chain, Parallel Tempering), Simulated Tempering (Expanded Ensemble Monte Carlo), and Multicanonical Monte Carlo (Adaptive Umbrella Sampling) are typical members of this family. Here we give a cross-disciplinary survey of these algorithms with special emphasis on the great f...

  9. Thin films of hydrogenated amorphous carbon (a-C:H) obtained through chemical vapor deposition assisted by plasma; Peliculas delgadas de carbono amorfo hidrogenado (a-C:H) obtenidas mediante deposito quimico de vapores asistido por plasma

    Energy Technology Data Exchange (ETDEWEB)

    Mejia H, J.A.; Camps C, E.E.; Escobar A, L.; Romero H, S.; Chirino O, S. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Muhl S, S. [IIM-UNAM, 04510 Mexico D.F. (Mexico)


    Films of hydrogenated amorphous carbon (a-C:H) were deposited using one source of microwave plasma with magnetic field (type ECR), using mixtures of H{sub 2}/CH{sub 4} in relationship of 80/20 and 95/05 as precursory gases, with work pressures of 4X10{sup -4} to 6x10{sup -4} Torr and an incident power of the discharge of microwaves with a constant value of 400 W. It was analyzed the influence among the properties of the films, as the deposit rate, the composition and the bonding types, and the deposit conditions, such as the flow rates of the precursory gases and the polarization voltage of the sample holders. (Author)

  10. Advanced TiC/a-C : H nanocomposite coatings deposited by magnetron sputtering

    NARCIS (Netherlands)

    Pei, Y.T.; Galvan, D.; Hosson, J.Th.M. De; Strondl, C.


    TiC/a-C:H nanocomposite coatings have been deposited by magnetron Sputtering. They consist of 2-5 nm TiC nanocrystallites embedded in the amorphous hydrocarbon (a-C:H) matrix. A transition from a Columnar to a glassy microstructure has been observed in the nanocomposite coatings with increasing subs

  11. a-C:H/a-C:H(N) thin film deposition using 2.45 GHz expanding surface wave sustained plasmas (United States)

    Hong, Suk-Ho; Douai, David; Berndt, Johannes; Winter, Jörg


    Thin film properties such as homogeneity (radial profiles), optical constants, carbon density in the film, and the surface structures are strongly dependent on deposition conditions. We have investigated a-C:H/a-C:H(N) thin film deposition by expanding Ar-CH4 and Ar/N2-CH4 surface wave sustained plasmas at a frequency of 2.45 GHz. The influence of the plasma parameters such as pressure, input power, gas mixture rate, and an external bias voltage on the change of the film properties is systematically studied. An external bias applied to the substrate leads to more dense and harder a-C:H films, i.e. change from soft polymer-like to hard diamond-like. Rutherford backscattering and atomic force microscope surface topology confirm the densification of the films.

  12. Anti-inflammatory activity of Arnica montana 6cH: preclinical study in animals. (United States)

    Macêdo, S B; Ferreira, L R; Perazzo, F F; Carvalho, J C


    The anti-inflammatory effect of Arnica montana 6cH was evaluated using acute and chronic inflammation models. In the acute, model, carrageenin-induced rat paw oedema, the group treated with Arnica montana 6cH showed 30% inhibition compared to control (P < 0.05). Treatment with Arnica 6cH, 30 min prior to carrageenin, did not produce any inhibition of the inflammatory process. In the chronic model, Nystatin-induced oedema, the group treated 3 days previously with Arnica montana 6cH had reduced inflammation 6 h after the inflammatory agent was applied (P < 0.05). When treatment was given 6 h after Nystatin treatment, there was no significant inhibitory effect. In a model based on histamine-induced increase of vascular permeability, pretreatment with Arnica montana 6cH blocked the action of histamine in increasing vascular permeability.

  13. Manganese(I)-Catalyzed Dispersion-Enabled C-H/C-C Activation. (United States)

    Meyer, Tjark H; Liu, Weiping; Feldt, Milica; Wuttke, Axel; Mata, Ricardo A; Ackermann, Lutz


    C-H/C-C Functionalizations were achieved with the aid of a versatile manganese(I) catalyst. Thus, an organometallic manganese-catalyzed C-H activation set the stage for silver-free C-H/C-C transformations with ample substrate scope and excellent levels of chemo-, site-, and diastereo-selectivities. The robust nature of the manganese(I) catalysis regime was reflected by the first C-H/C-C functionalization on amino acids under racemization-free reaction conditions. Detailed experimental and computational mechanistic studies provided strong evidence for a facile C-H activation and a rate-determining C-C cleavage, with considerable contribution from London dispersion interactions.

  14. Probing the limits of ligand steric bulk: backbone C-H activation in a saturated N-heterocyclic carbene. (United States)

    Phillips, Nicholas; Tirfoin, Remi; Aldridge, Simon


    The consequences of extremely high steric loading have been probed for late transition metal complexes featuring the expanded ring N-heterocyclic carbene 6-Dipp. The reluctance of this ligand to form 2:1 complexes with d-block metals (rationalised on the basis of its percentage buried volume, % Vbur , of 50.8%) leads to C-H and C-N bond activation processes driven by attack at the backbone β-CH2 unit. In the presence of Ir(I) (or indeed H(+) ) the net result is the formation of an allyl formamidine fragment, while Au(I) brings about an additional ring (re-)closure step via nucleophilic attack at the coordinated alkene. The net transformation of 6-Dipp in the presence of [(6-Dipp)Au](+) represents to our knowledge the first example of backbone C-H activation of a saturated N-heterocyclic carbene, proceeding in this case via a mechanism which involves free carbene in addition to the Au(I) centre. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Diamond-like a-C:H coatings deposited in a non-self-sustained discharge with plasma cathode (United States)

    Gavrilov, N. V.; Mamaev, A. S.; Kaĭigorodov, A. S.


    Hydrogenated amorphous carbon (a-C:H) coatings have been obtained by means of acetylene decomposition in a non-self-sustained periodic pulse discharge (2A, 50 kHz, 10 μs) with hollow cathode. The discharge operation was maintained by plasma cathode emission with grid stabilization based on dc glow discharge. Using the proposed method, it is possible to control the deposition conditions (total pressure of the Ar + C2H2 mixture, partial pressure of C2H2, ion current density, carbon ion energy) within broad limits, to apply a-C:H coatings onto large-area articles, and to perform deposition in one technological cycle with ion etching and ion implantation treatments aimed at improving the adhesion of coatings to substrates (Ti, Al, stainless steel, VK8 hard alloy) at temperatures below 150°C. Results of determining the deposition rate (1-8 μm), the nanohardness of coatings (up to 70 GPa), and the fraction of sp 3 bonds (25-70%) in the diamond-like coating material are presented.

  16. Molecular Engineering of Mechanochromic Materials by Programmed C-H Arylation: Making a Counterpoint in the Chromism Trend. (United States)

    Wu, Jie; Cheng, Yangyang; Lan, Jingbo; Wu, Di; Qian, Shengyou; Yan, Lipeng; He, Zhen; Li, Xiaoyu; Wang, Kai; Zou, Bo; You, Jingsong


    The development of facile methods for screening organic functional molecules through C-H bond activation is a revolutionary trend in materials research. The prediction of mechanochromism as well as mechanochromic trends of luminogens is an appealing yet challenging puzzle. Here, we present a strategy for the design of mechanochromic luminogens based on the dipole moment of donor-acceptor molecules. For this purpose, a highly efficient route to 2,7-diaryl-[1,2,4]triazolo[1,5-a]pyrimidines (2,7-diaryl-TAPs) has been established through programmed C-H arylation, which unlocks a great opportunity to rapidly assemble a library of fluorophores for the discovery of mechanochromic regularity. Molecular dipole moment can be employed to explain and further predict the mechanochromic trends. The 2,7-diaryl-TAPs with electron-donating groups on the 2-aryl and electron-withdrawing groups on the 7-aryl possess a relatively small dipole moment and exhibit a red-shifted mechanochromism. When the two aryls are interchanged, the resulting luminogens have a relatively large dipole moment and display a blue-shifted mechanochromism. Seven pairs of isomers with opposite mechanochromic trends are presented as illustrative examples. The aryl-interchanged congeners with a bidirectional emission shift are structurally similar, which provides an avenue for understanding in-depth the mechanochromic mechanism.

  17. Tagging the Untaggable: A Difluoroalkyl-Sulfinate Ketone-Based Reagent for Direct C-H Functionalization of Bioactive Heteroarenes. (United States)

    Gnaim, Samer; Scomparin, Anna; Li, Xiuling; Baran, Phil S; Rader, Christoph; Satchi-Fainaro, Ronit; Shabat, Doron


    We have developed a new difluoroalkyl ketal sulfinate salt reagent suitable for direct derivatization of heteroarene C-H bonds. The reagent is capable of introducing a ketone functional group on heteroarene bioactive compounds via a one-pot reaction. Remarkably, in three examples the ketone analog and its parent drug had almost identical cytotoxicity. In a representative example, the ketone analog was bioconjugated with a delivery vehicle via an acid-labile semicarbazone linkage and with a photolabile protecting group to produce the corresponding prodrug. Controlled release of the drug-ketone analog was demonstrated in vitro for both systems. This study provides a general approach to obtain taggable ketone analogs directly from bioactive heteroarene compounds with limited options for conjugation. We anticipate that this sodium ketal-sulfinate reagent will be useful for derivatization of other heteroarene-based drugs to obtain ketone-taggable analogs with retained efficacy.

  18. Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru-based Catalyst and Alcohols

    KAUST Repository

    Poater, Albert


    Density functional theory calculations have been used to investigate the reaction mechanism for [(C6H6)(PCy3)(CO) RuH](+) (1; Cy, cyclohexyl) mediated alkylation of indene substrate using ethanol as solvent. According to Yi et al. [ Science 2011, 333, 1613] the plausible reaction mechanism involves a cationic Rualkenyl species, which is initially formed from 1 with two equivalents of the olefin substrate via the vinylic C-H activation and an alkane elimination step. Once the active catalytic species is achieved the oxidative addition step is faced. The latter step together with the next C-C bond formation might display the upper barrier of the catalytic cycle. Having these experimental insights at hand, we investigated in detail the whole reaction pathway using several computational DFT approaches including alternative pathways, higher in energy.

  19. Understanding the differential performance of Rh2(esp)2 as a catalyst for C-H amination. (United States)

    Zalatan, David N; Du Bois, J


    Catalytic amination of saturated C-H bonds is performed efficiently with the use of Rh(2)(esp)(2). Efforts to identify pathways for catalyst degradation and/or arrest have revealed a single-electron oxidation event that gives rise to a red-colored, mixed-valence dimer, [Rh(2)(esp)(2)](+). This species is fortuitously reduced by carboxylic acid, a byproduct generated in the reaction cycle with each turnover of the diacyloxyiodine oxidant. These findings have led to the conclusion that the high performance of Rh(2)(esp)(2) is due in part to the superior kinetic stability of its one-electron oxidized form relative to other dimeric Rh complexes.

  20. Valuing Convertible Bonds Based on LSRQM Method

    Directory of Open Access Journals (Sweden)

    Jian Liu


    Full Text Available Convertible bonds are one of the essential financial products for corporate finance, while the pricing theory is the key problem to the theoretical research of convertible bonds. This paper demonstrates how to price convertible bonds with call and put provisions using Least-Squares Randomized Quasi-Monte Carlo (LSRQM method. We consider the financial market with stochastic interest rates and credit risk and present a detailed description on calculating steps of convertible bonds value. The empirical results show that the model fits well the market prices of convertible bonds in China’s market and the LSRQM method is effective.

  1. Rh(III)-Catalyzed Cascade Annulation/C-H Activation of o-Ethynylanilines with Diazo Compounds: One-Pot Synthesis of Benzo[a]carbazoles via 1,4-Rhodium Migration. (United States)

    Guo, Songjin; Yuan, Kai; Gu, Meng; Lin, Aijun; Yao, Hequan


    A Rh(III)-catalyzed cascade annulation/C-H activation of o-ethynylanilines with diazo compounds has been developed. This concise method allows for the rapid formation of a number of benzo[a]carbazoles in high yields, exhibiting good functional group tolerance and scalability. The key to the success of this approach involves one C-N bond and two C-C bond formation, and an aryl-to-aryl 1,4-rhodium migration.

  2. Study of the hydrogen behavior in amorphous hydrogenated materials of type a - C:H and a - SiC:H facing fusion reactor plasma; Etude du comportament de l`hydrogene dans des materiaux amorphes hydrogenes de type a - C:H et a - SiC:H devant faire face au plasma des reacteurs a fusion

    Energy Technology Data Exchange (ETDEWEB)

    Barbier, G. [Lyon-1 Univ., 69 - Villeurbanne (France). Inst. de Physique Nucleaire


    Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. First, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce these interactions, we have selected two amorphous hydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a - SiC:H substrate can be beneficial in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a-SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a - C:H and a - SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modelling of hydrogen diffusion under irradiation has been also proposed. (author) 176 refs.

  3. Identification of nanoscale structure and morphology reconstruction in oxidized a-SiC:H thin films

    Energy Technology Data Exchange (ETDEWEB)

    Vasin, A.V.; Rusavsky, A.V.; Nazarov, A.N.; Lysenko, V.S.; Lytvyn, P.M.; Strelchuk, V.V. [Lashkaryov Institute of Semiconductor Physics, 41 Nauki Pr., Kiev 03028 (Ukraine); Kholostov, K.I.; Bondarenko, V.P. [Belarusian State University of Informatics and Radioelectronics, 6P. Brovki Str., Minsk 220013 (Belarus); Starik, S.P. [Bakul Institute of Superhard Materials, 2 Avtzavodskaya Str., Kiev 04074 (Ukraine)


    Highlights: Black-Right-Pointing-Pointer Increase of magnetron discharge power results in densification of a-SiC:H thin films. Black-Right-Pointing-Pointer The denser a-SiC:H material the better resistance to oxidation by oxygen. Black-Right-Pointing-Pointer Oxidation of soft a-SiC:H films can result in increase of electric conductivity. Black-Right-Pointing-Pointer Formation of graphitic clusters was found in a-SiC:H after annealing in oxygen. - Abstract: Oxidation behavior of a-SiC:H layers deposited by radio-frequency magnetron sputtering technique was examined by Kelvin probe force microscopy (KPFM) in combination with scanning electron microscopy, Fourier-transform infra-red spectroscopy and submicron selected area Raman scattering spectroscopy. Partially oxidized a-SiC:H samples (oxidation at 600 Degree-Sign C in oxygen) were examined to clarify mechanism of the oxidation process. Nanoscale and microscale morphological defects (pits) with dimension of about 50 nm and several microns respectively have appeared after thermal treatment. KPFM measurements exhibited the surface potential of the material in micro pits is significantly smaller in comparison with surrounding material. Submicron RS measurements indicates formation of graphite-like nano-inclusions in the pit defects. We conclude that initial stage of oxidation process in a-SiC:H films takes place not homogeneously throughout the layer but it is initiated in local nanoscale regions followed by spreading over all layer.

  4. Bond Issues. (United States)

    Pollack, Rachel H.


    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  5. High-Pressure Plasma Deposition of a-C:H Films by Dielectric-Barrier Discharge

    Institute of Scientific and Technical Information of China (English)

    刘昌俊; 李阳; 杜海燕; 艾宝都


    The fabrication of a-C:H films from methane has been performed using dielectric-barrier discharges at atmospheric pressure. The effect of combined-feed gas, such as carbon dioxide,carbon monoxide or acetylene on the formation of a-C:H films has been investigated. It hasbeen demonstrated that the addition of carbon monoxide or acetylene into methane leads to aremarkable improvement in the fabrication of a-C:H films. The characterization of carbon filmobtained has been conducted using FT-IR, Raman and SEM.


    NARCIS (Netherlands)



    Extended Huckel (EHT) calculations have been used to discuss the two alternative sigma-bond C-H metathesis reactions which occur with organo-lanthanide (Ln = Y, Lu) compounds. The two reactions lead either to H/H (H/D) exchange or to metalation and have been modelled by studying the interaction of a

  7. Monte Carlo fundamentals

    Energy Technology Data Exchange (ETDEWEB)

    Brown, F.B.; Sutton, T.M.


    This report is composed of the lecture notes from the first half of a 32-hour graduate-level course on Monte Carlo methods offered at KAPL. These notes, prepared by two of the principle developers of KAPL`s RACER Monte Carlo code, cover the fundamental theory, concepts, and practices for Monte Carlo analysis. In particular, a thorough grounding in the basic fundamentals of Monte Carlo methods is presented, including random number generation, random sampling, the Monte Carlo approach to solving transport problems, computational geometry, collision physics, tallies, and eigenvalue calculations. Furthermore, modern computational algorithms for vector and parallel approaches to Monte Carlo calculations are covered in detail, including fundamental parallel and vector concepts, the event-based algorithm, master/slave schemes, parallel scaling laws, and portability issues.

  8. Monte Carlo methods


    Bardenet, R.


    ISBN:978-2-7598-1032-1; International audience; Bayesian inference often requires integrating some function with respect to a posterior distribution. Monte Carlo methods are sampling algorithms that allow to compute these integrals numerically when they are not analytically tractable. We review here the basic principles and the most common Monte Carlo algorithms, among which rejection sampling, importance sampling and Monte Carlo Markov chain (MCMC) methods. We give intuition on the theoretic...

  9. Rh(I)-Catalyzed Arylation of Heterocycles via C-H Bond Activation: Expanded Scope Through Mechanistic Insight

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Berman, Ashley; Bergman, Robert; Ellman, Jonathan


    A practical, functional group tolerant method for the Rh-catalyzed direct arylation of a variety of pharmaceutically important azoles with aryl bromides is described. Many of the successful azole and aryl bromide coupling partners are not compatible with methods for the direct arylation of heterocycles using Pd(0) or Cu(I) catalysts. The readily prepared, low molecular weight ligand, Z-1-tert-butyl-2,3,6,7-tetrahydrophosphepine, which coordinates to Rh in a bidentate P-olefin fashion to provide a highly active yet thermally stable arylation catalyst, is essential to the success of this method. By using the tetrafluoroborate salt of the corresponding phosphonium, the reactions can be assembled outside of a glove box without purification of reagents or solvent. The reactions are also conducted in THF or dioxane, which greatly simplifies product isolation relative to most other methods for direct arylation of azoles employing high-boiling amide solvents. The reactions are performed with heating in a microwave reactor to obtain excellent product yields in two hours.

  10. Copper-catalyzed direct amination of quinoline N-oxides via C-H bond activation under mild conditions. (United States)

    Zhu, Chongwei; Yi, Meiling; Wei, Donghui; Chen, Xuan; Wu, Yangjie; Cui, Xiuling


    A highly efficient and concise one-pot strategy for the direct amination of quinoline N-oxides via copper-catalyzed dehydrogenative C-N coupling has been developed. The desired products were obtained in good to excellent yields for 22 examples starting from the parent aliphatic amines. This methodology provides a practical pathway to 2-aminoquinolines and features a simple system, high efficiency, environmental friendliness, low reaction temperature, and ligand, additives, base, and external oxidant free conditions.

  11. Activation of propane C-H and C-C bonds by gas-phase Pt atom: a theoretical study

    National Research Council Canada - National Science Library

    Li, Fang-Ming; Yang, Hua-Qing; Ju, Ting-Yong; Li, Xiang-Yuan; Hu, Chang-Wei


    The reaction mechanism of the gas-phase Pt atom with C(3)H(8) has been systematically investigated on the singlet and triplet potential energy surfaces at CCSD(T)//BPW91/6-311++G(d, p), Lanl2dz level...

  12. Amine Catalyzed Solvent C-H Bond Activation as Deactivation Route for Cationic Decamethylzirconocene Olefin Polymerization Catalysts

    NARCIS (Netherlands)

    Rios, Itzel Guerrero; Novarino, Elena; van der Veer, Siebe; Hessen, Bart; Bouwkamp, Marco W.


    [Cp(2)ZrMe)(+) + Me(3)N + C(6)H(6) down arrow TS2 Cp(2)ZrMePh + (Me(3)NH](+) down arrow TS3 [Cp(2)ZrPh](+) + Me(3)N + CH(4) The C-D activation of bromobenzene-d(5), by [CP(2)*ZrMe(BrC(6)D(5)-kappa Br)][B(C(6)F(5))(4)] to form sigma-aryl complex [Cp(2)*Zr(2-BrC(6)D(4)-kappa(2)Br,C)][B(C(6)F(5))(4)

  13. Activation of C-H bonds of arenes: selectivity and reactivity in bis(pyridyl) platinum(II) complexes. (United States)

    Zhang, Fenbao; Kirby, Christopher W; Hairsine, Douglas W; Jennings, Michael C; Puddephatt, Richard J


    The reaction of [PtMe2(NN)] and B(C6F5)3/H2O in CF3CH2OH with arenes Ar-H gives [PtAr{HOB(C6F5)3}(LL)] if the bis(pyridyl) ligand NN forms a six-membered, but not five-membered, chelate ring; methyl-substituted arenes give selectivity for metalation of meta > para > ortho, but methoxy-substituted arenes give ortho > meta, para.

  14. Rapid synthesis of fused N-heterocycles by transition-metal-free electrophilic amination of arene C-H bonds. (United States)

    Gao, Hongyin; Xu, Qing-Long; Yousufuddin, Muhammed; Ess, Daniel H; Kürti, László


    We disclose an efficient and operationally simple protocol for the preparation of fused N-heterocycles starting from readily available 2-nitrobiaryls and PhMgBr under mild conditions. More than two dozen N-heterocycles, including two bioactive natural products, have been synthesized using this method. A stepwise electrophilic aromatic cyclization mechanism was proposed by DFT calculations.

  15. Amine Catalyzed Solvent C-H Bond Activation as Deactivation Route for Cationic Decamethylzirconocene Olefin Polymerization Catalysts

    NARCIS (Netherlands)

    Rios, Itzel Guerrero; Novarino, Elena; van der Veer, Siebe; Hessen, Bart; Bouwkamp, Marco W.


    [Cp(2)ZrMe)(+) + Me(3)N + C(6)H(6) down arrow TS2 Cp(2)ZrMePh + (Me(3)NH](+) down arrow TS3 [Cp(2)ZrPh](+) + Me(3)N + CH(4) The C-D activation of bromobenzene-d(5), by [CP(2)*ZrMe(BrC(6)D(5)-kappa Br)][B(C(6)F(5))(4)] to form sigma-aryl complex [Cp(2)*Zr(2-BrC(6)D(4)-kappa(2)Br,C)][B(C(6)F(5))(4)] i

  16. Copper-Dioxygen Complex Mediated C-H Bond Oxygenation: Relevance for Particulate Methane Monooxygenase (pMMO)


    Himes, Richard A.; Karlin, Kenneth D.


    Particulate methane monooxygenase (pMMO), an integral membrane protein found in methanotrophic bacteria, catalyzes the oxidation of methane to methanol. Expression and greater activity of the enzyme in the presence of copper ion suggest that pMMO is a cuprous metalloenzyme. Recent advances – especially the first crystal structures of pMMO – have energized the field, but the nature of the active site(s) and the mechanism of methane oxidation remain poorly understood – yet hotly contested. Here...

  17. Initial Stages in the Rhodium(III)-Catalyzed C-H Bond Activation of Primary Alcohols in Aqueous Solution

    DEFF Research Database (Denmark)

    Eriksen, J.; Monsted, L.; Monsted, O.


    ,4,8,11-tetraazacyclotetradecane) cation. The hydride complex is stable for extended periods of time in acidic solution in the absence of oxidants. In basic solutions a series of base-catalyzed reactions take place to yield ultimately the same mixture of [Rh(cycb)(OH)(2)](+) isomers as produced by base hydrolysis of the trans...

  18. Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C-H Activation

    Energy Technology Data Exchange (ETDEWEB)

    Ellman, Jonathan A.; Colby, Denise; Bergman, Robert


    A convenient one-pot C-H alkenylation/electrocyclization/aromatization sequence has been developed for the synthesis of highly substituted pyridine derivatives from alkynes and {alpha},{beta}-unsaturated N-benzyl aldimines and ketimines that proceeds through dihydropyridine intermediates. A new class of ligands for C-H activation was developed, providing broader scope for the alkenylation step than could be achieved with previously reported ligands. Substantial information was obtained about the mechanism of the reaction. This included the isolation of a C-H activated complex and its structure determination by X-ray analysis; in addition, kinetic simulations using the Copasi software were employed to determine rate constants for this transformation, implicating facile C-H oxidative addition and slow reductive elimination steps.

  19. Elemental (C, H, N) composition of zooplankton from north Arabian Sea

    Digital Repository Service at National Institute of Oceanography (India)

    Matondkar, S.G.P.; Bhat, K.L.; Ansari, Z.A.; Parulekar, A.H.

    Zooplankton samples collected from north Arabian Sea during March 1992 were analysed for elemental (C,H,N) composition. Estimated carbon, hydrogen and nitrogen concentrations displayed variations among different groups but their ratios were nearly...

  20. Exploring Monte Carlo methods

    CERN Document Server

    Dunn, William L


    Exploring Monte Carlo Methods is a basic text that describes the numerical methods that have come to be known as "Monte Carlo." The book treats the subject generically through the first eight chapters and, thus, should be of use to anyone who wants to learn to use Monte Carlo. The next two chapters focus on applications in nuclear engineering, which are illustrative of uses in other fields. Five appendices are included, which provide useful information on probability distributions, general-purpose Monte Carlo codes for radiation transport, and other matters. The famous "Buffon's needle proble

  1. Multidirectional Synthesis of Substituted Indazoles via Iridium-Catalyzed C-H Borylation. (United States)

    Sadler, Scott A; Hones, Andrew C; Roberts, Bryan; Blakemore, David; Marder, Todd B; Steel, Patrick G


    In the absence of a steric directing group, iridium-catalyzed C-H borylation of N-protected indazoles occurs rapidly and selectively at C-3 and the resulting boronate esters can be utilized in a range of downstream conversions. The functional group tolerance of the iridium-catalyzed C-H borylation reaction enables simple and efficient multidirectional syntheses of substituted indazoles to be realized.

  2. Mild Cobalt(III)-Catalyzed Allylative C-F/C-H Functionalizations at Room Temperature. (United States)

    Zell, Daniel; Müller, Valentin; Dhawa, Uttam; Bursch, Markus; Presa, Rubén Rubio; Grimme, Stefan; Ackermann, Lutz


    Sustainable, cobalt-catalyst enabled, synthetically significant C-F/C-H functionalizations were achieved with an ample substrate scope at an ambient temperature of 25 °C, thereby delivering perfluoroallylated heteroarenes. Detailed experimental and computational mechanistic studies on the C-F/C-H functionalizations provided strong support for a facile C-F cleavage. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Tuning the reactivity of an actor ligand for tandem CO2 and C-H activations: from spectator metals to metal-free. (United States)

    Annibale, Vincent T; Dalessandro, Daniel A; Song, Datong


    The 4,5-diazafluorenide ligand (L(-)) serves as an actor ligand in the formal insertion of CO2 into a C-H bond remote from the metal center. With the Ru(II) complex of L(-) as the starting point, Rh(III), Rh(I), and Cu(I) were used as spectator metal centers to tune the reactivity of the actor ligand toward CO2. In the case of Rh(III)-diazafluorenide a room temperature reversible activation of CO2 was observed, similar to the isoelectronic Ru(II) analogue. In the case of Rh(I)- and Cu(I)-diazafluorenide CO2 is trapped by the formation of dinuclear carboxylate complexes and diazafluorene (LH). The spectator metal center could even be replaced entirely with an organic group allowing for the first metal-free reversible tandem CO2 and C-H activation.

  4. Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols

    KAUST Repository

    Ranjit, Sadananda


    We report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C-H bond activation in the presence of stoichiometric CuI, 2,2′-bipyridine and Na 2CO 3. We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper-thiolate complex [(L)Cu(SR)] (L: nitrogen-based bidentate ligand such as 2,2′-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including β-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis. © 2011 American Chemical Society.

  5. Structure and Friction Behavior of CrNx/a-C:H Nanocomposite Films

    Directory of Open Access Journals (Sweden)

    Lunlin Shang


    Full Text Available CrN and CrNx/a-C:H nanocomposite films were deposited on Si substrates by the magnetron sputtering technique. The structure, chemical state, and friction behavior of the CrNx/a-C:H films prepared at various CH4 content were studied systematically. The CrN film shows strong (111 and (220 orientation, while the CrNx/a-C:H films consist of the nanocrystalline CrNx or Cr particles embedded in an amorphous hydrocarbon (a-C:H matrix and show weak diffraction peaks, which is in accordance with the XPS analysis results. The typical Raman D and G peaks are observed, indicating that the separated amorphous carbon or CNx phase appears in the CrNx/a-C:H films. However, no chromium carbide was observed in all the as-deposited samples. From the SEM graphs, all the deposited films depicted a dense and compact microstructure with well-attached interface with the substrate. The average friction coefficient of the CrNx/a-C:H films largely decreased with increasing CH4 content.

  6. DFT Mechanistic Study of Rh(III)-Catalyzed [3 + 2]/[5 + 2] Annulation of 4-Aryl-1,2,3-triazoles and Alkynes Unveils the Dual C-H Activation Strategy. (United States)

    Zhang, Zhongchao; Yang, Shengwen; Li, Juan; Liao, Xiaojian


    Li and co-workers recently developed a dual C-H bond activation strategy, using a Rh(III) catalyst, for [3 + 2]/[5 + 2] annulation of primary 4-aryl-1,2,3-triazoles and alkynes. The Rh(III)-catalyzed dual annulation of 4-aryl-1,2,3-triazoles and alkynes is challenging because only single annulation is achieved using Rh(II) and Ni(0) catalysts. Intrigued by the novel strategy, we performed a density functional theory study to unravel this challenging dual C-H bond activation. A Friedel-Crafts type mechanism proved be more favorable than a concerted metalation-deprotonation (CMD) mechanism for the first C-H bond activation. The second C-H bond activation proceeded via a CMD mechanism. More importantly, the calculation explained why only AgSbF6, among several candidates, performed perfectly, whereas others failed, and why the dual annulation of 4-aryl-1,2,3-triazoles with alkynes was achieved with a Rh(III) catalyst but not with Rh(II) and Ni(0) catalysts. Due to the active catalyst being [Cp*Rh(OAc)](+), AgSbF6, in which SbF6(-) is a stable anion, among several candidates performed perfectly. The success of the Rh(III)-catalyzed dual C-H bond activation has two origins: (i) the active catalyst [Cp*Rh(OAc)](+) is more stable than Cp*Rh(OAc)2 when the Ag salt is AgSbF6, and this facilitates the first alkyne insertion; and (ii) a rhodium-carbene is easily formed.

  7. Thermal Modification of a-SiC:H Films Deposited by Plasma Enhanced Chemical Vapour Deposition from CH4+SiH4 Mixtures

    Institute of Scientific and Technical Information of China (English)

    刘玉学; 王宁会; 刘益春; 申德振; 范希武; 李灵燮


    The effects of thermal annealing on photoluminescence (PL) and structural properties of a-Si1-xCx :H films deposited by plasma enhanced chemical vapour deposition from CH4+SiH4 mixtures are studied by using infrared, PL and transmittance-reflectance spectra. In a-SiC:H network, high-temperature annealing gives rise to the effusion of hydrogen from strongly bonded hydrogen in SiH, SiH2, (SiH2)n, SiCHn and CHn configurations and the break of weak C-C, Si-Si and C-Si bonds. A structural rearrangement will occur, which causes a significant correlation of the position and intensity of the PL signal with the annealing temperature. The redshift of the PL peak is related to the destruction of the confining power of barriers. However, the PL intensity does not have a significant correlation with the annealing temperature for a C-rich a-SiC:H network, which refers to the formation of π-bond cluster as increasing carbon content. It is indicated that the thermal stability of C-rich a-Si1-xCx:H films is better than that of Si-like a-Si1-xCx :H films.

  8. A Motion Algorithm of Three-Bond Unit in the Monte Carlo Simulation of Comb Polymer%梳型高分子Monte Carlo模拟中三键交联单元运动的算法

    Institute of Scientific and Technical Information of China (English)

    许文彬; 韩兆让; 王宏; 田卫星; 陈仲


    提出了一种用于梳型高分子中三键交联单元运动的新算法,用新算法统计了梳型高分子的静态和动态性质,并与Larson等人的单位置键长涨落算法进行了比较.经检验证明,梳型高分子的静态性质——均方回转半径对应分子量的双对数函数呈直线关系,与Rouault与Shiokawa的模拟结果吻合;梳型高分子的3个动态性质——质量中心扩散均方值、链节运动自相关函数与链节相对于质量中心运动相关函数随时间变化的趋势符合Rouse-Zimm理论;在三维格子模型中新算法可使梳型高分子链中含三键交联单元的运动效率提高1倍以上.%A motion algorithm for three-bond units in comb polymer was proposed. The static and dynamic properties of comb polymer were calculated using this algorithm, and the algorithm was compared with the bond fluctuation model proposed by Larson etc. The results show that the gyration radius of the comb polymer and the molecular weight are lg-lg type linearity, the trend of the mean-square center-of mass displacement, mean-square displacement and the mean-square center-of-mass displacement of comb polymer changing with time are coincided with the Rouse-Zimm theory, the simulation efficiency of the comb polymer is obviously improved more than one time in three-dimensional lattice model. The problem that the three-bond units of comb polymer can not move in Lason's method in two-dimensional lattice model was solved using the new algorithm.

  9. SAN CARLOS APACHE PAPERS. (United States)



  10. San Carlo Operaen

    DEFF Research Database (Denmark)

    Holm, Bent


    En indplacering af operahuset San Carlo i en kulturhistorisk repræsentationskontekst med særligt henblik på begrebet napolalità.......En indplacering af operahuset San Carlo i en kulturhistorisk repræsentationskontekst med særligt henblik på begrebet napolalità....

  11. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock


    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  12. Hydrogen-bonded sheets in benzylmethylammonium hydrogen maleate. (United States)

    Santacruz, Lynay; Abonia, Rodrigo; Cobo, Justo; Low, John N; Glidewell, Christopher


    In the title compound, C(8)H(12)N(+).C(4)H(3)O(4)(-), there is a short and almost linear but asymmetric O-H...O hydrogen bond in the anion. The ions are linked into C(2)(2)(6) chains by two short and nearly linear N-H...O hydrogen bonds and the chains are further weakly linked into sheets by a single C-H...O hydrogen bond.

  13. Rh(III)-Catalyzed Carbocyclization of 3-(Indolin-1-yl)-3-oxopropanenitriles with Alkynes and Alkenes through C-H Activation. (United States)

    Zhou, Tao; Wang, Yanwei; Li, Bin; Wang, Baiquan


    Rh(III)-catalyzed carbocyclization reactions of 3-(indolin-1-yl)-3-oxopropanenitriles with alkynes and alkenes have been developed to form 1,7-fused indolines through C-H activation. These reactions have a broad range of substrates and high yields. Unsymmetrical aryl-alkyl substituted alkynes proceeded smoothly with high regioselectivity. Electron-rich alkynes could undergo further oxidative coupling reaction to form polycyclic compounds. For alkenes, 1,2-dihydro-4H-pyrrolo[3,2,1-ij]quinolin-4-ones were formed via C(sp(2))-H bond alkenylation and C(sp(2))-H, C(sp(3))-H oxidative coupling reactions.

  14. N-Doped Cationic PAHs by Rh(III)-Catalyzed Double C-H Activation and Annulation of 2-Arylbenzimidazoles with Alkynes. (United States)

    Villar, José M; Suárez, Jaime; Varela, Jesús A; Saá, Carlos


    A novel class of N-doped cationic PAHs (polycyclic aromatic hydrocarbons) bearing the benzo[c,d]fluoranthene scaffold has been synthesized by the Rh(III)-catalyzed double-oxidative annulation of 2-arylbenzimidazoles with alkynes. The overall process involves a double C-N bond formation through a double C-H/N-H functionalization.The solid-state structures and electronic properties of the new N-doped PAHs were analyzed. These cationic azapolycycles were readily reduced in the presence of LiAlH4 or by the addition of PhLi to give interesting phenyl and diphenylmethanediamine derivatives.

  15. Isotopic Effects on Stereodynamics of the C+ + H2 → CH+ + H Reaction (United States)

    Guo, Lu; Yang, Yun-Fan; Fan, Xiao-Xing; Ma, Feng-Cai; Li, Yong-Qing


    The effects of isotope substitution on stereodynamic properties for the reactions {C}++{H}2/{H D}/{H T}\\to {{C H}}++H/D/T have been studied applying a quasi classical trajectory method occurring on the new ground state {{C H}}2+ potential energy surface [J. Chem. Phys. 142 (2015) 124302]. In the center of mass coordinates applying the quasi classical trajectory method to investigate the orientation and the alignment of the product molecule. Differential cross section and three angle distribution functions P(θr), P(ϕr), P( {θ }r,{φ }r ) on the potential energy surface that fixed the collision energy with a value is 40 kcal/mol have been studied. The isotope effect becomes more and more important with the reagent molecules H 2 changing into HD and HT. P({θ }r,{φ }r) as the joint probability density function of both polar angles θ r and ϕ r , which can illustrate more detailed dynamics information. The isotope effect is obvious influence on the properties of stereodynamics in the reactions of {C}++{H}2/{H D}/{H T}\\to {{C H}}++H/D/T. Supported by the National Natural Science Foundation of China under Grant Nos. 11474141, 11274149, 11544015, the Program for Liaoning Excellent Talents in University under Grant No. LJQ2015040, and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (2014-1685)

  16. MORSE Monte Carlo code

    Energy Technology Data Exchange (ETDEWEB)

    Cramer, S.N.


    The MORSE code is a large general-use multigroup Monte Carlo code system. Although no claims can be made regarding its superiority in either theoretical details or Monte Carlo techniques, MORSE has been, since its inception at ORNL in the late 1960s, the most widely used Monte Carlo radiation transport code. The principal reason for this popularity is that MORSE is relatively easy to use, independent of any installation or distribution center, and it can be easily customized to fit almost any specific need. Features of the MORSE code are described.

  17. Difluoroacetic Acid as a New Reagent for Direct C-H Difluoromethylation of Heteroaromatic Compounds

    DEFF Research Database (Denmark)

    Thanh Tung, Truong; Christensen, Søren Brøgger; Nielsen, John


    A technically simple procedure for direct C-H difluoromethylation of heteroaromatic compounds using off-the-shelf difluoroacetic acid as the difluoromethylating reagent has been developed. Mono-difluoromethylation versus bis-difluoromethylation is controlled as the result of the reaction temperat......A technically simple procedure for direct C-H difluoromethylation of heteroaromatic compounds using off-the-shelf difluoroacetic acid as the difluoromethylating reagent has been developed. Mono-difluoromethylation versus bis-difluoromethylation is controlled as the result of the reaction...

  18. Behavior of rats treated with Rhus toxicodendron 200cH Conducta da ratones tratados con Rhus toxicodendron 200cH Conduta de ratos tratados com Rhus toxicodendron 200cH

    Directory of Open Access Journals (Sweden)

    Leoni Villano Bonamin


    Full Text Available One of the main pathogenetic characteristics of Rhus toxicodendron (Rhus-t is the presence of articular pain and aggravation on standing, which improve only by motion. The present study proposes an experimental model to evaluate the action of Rhus-t 200cH. Rats were divided into 3 groups according to treatment received (Rhus-t, diazepam and water; each group was further divided into two sub-groups according to the initial pattern of behavior (hyperactive and hypoactive as assessed by open-field procedure. A second evaluation of behavior performed 24 hours later pointed out to the effects of the medications under study. Results were analyzed through Kruskal-Wallis/Dunn’s test, with a level of significance p=0.05. Keywords: Rhus toxicodendron; Animal behavior; Open-field; Idiosyncrasy.   Conduta de ratos tratados com Rhus toxicodendron 200cH Resumo Uma das características patogenéticas principais de Rhus toxicodendron (Rhus-t é a presença de dor articular e agravação em pé, melhorando exclusivamente com o movimento. O presente estudo propõe um modelo experimental para avaliar a ação de Rhus-t 200cH. Ratos foram divididos em 3 grupos de tratamento (Rhus-t, diazepam e água; cada grupo doi subdividido em 2 subgrupos de acordo com o padrão inicial de conduta (hiper e hipoativos em procedimento de campo aberto. Uma segunda avaliação da conduta, realizada 24 horas após, indicou o efeito dos medicamentos sob estudo. Os resultados foram analisados pelo teste de Kruskal-Ealis/Dunn com nível de significância p=0,05. Palavras-chave: Rhus toxicodendron; comportamento animal; Campo aberto; idiossincrasia.   Conducta da ratones tratados con Rhus toxicodendron 200cH Resumen Una de las principales características patogenéticas de Rhus toxicodendron (Rhus-t es la presencia de dolor articular y

  19. Simultaneous structure-activity studies and arming of natural products by C-H amination reveal cellular targets of eupalmerin acetate (United States)

    Li, Jing; Cisar, Justin S.; Zhou, Cong-Ying; Vera, Brunilda; Williams, Howard; Rodríguez, Abimael D.; Cravatt, Benjamin F.; Romo, Daniel


    Natural products have a venerable history of, and enduring potential for the discovery of useful biological activity. To fully exploit this, the development of chemical methodology that can functionalize unique sites within these complex structures is highly desirable. Here, we describe the use of rhodium(II)-catalysed C-H amination reactions developed by Du Bois to carry out simultaneous structure-activity relationship studies and arming (alkynylation) of natural products at ‘unfunctionalized’ positions. Allylic and benzylic C-H bonds in the natural products undergo amination while olefins undergo aziridination, and tertiary amine-containing natural products are converted to amidines by a C-H amination-oxidation sequence or to hydrazine sulfamate zwitterions by an unusual N-amination. The alkynylated derivatives are ready for conversion into cellular probes that can be used for mechanism-of-action studies. Chemo- and site-selectivity was studied with a diverse library of natural products. For one of these—the marine-derived anticancer diterpene, eupalmerin acetate—quantitative proteome profiling led to the identification of several protein targets in HL-60 cells, suggesting a polypharmacological mode of action.

  20. DFT Mechanistic Study of the Selective Terminal C-H Activation of n-Pentane with a Tungsten Allyl Nitrosyl Complex

    KAUST Repository

    Lee, Richmond


    Mechanistic insights into the selective C-H terminal activation of n-pentane with tungsten allyl nitrosyl complex reported by Legzdins were gained by employing density functional theory with B3LYP hybrid functional. Using Bader’s atom in molecules (AIM) analysis on the elementary steps of the hydrogen transfer process, TS1 and TS2, it was observed that the calculated H-transfer models were closely similar to Hall’s metal-assisted σ-bond metathesis through bond critical point (BCP) comparisons. One distinguishable feature was the fact that the formal oxidation state of the W changed in the concerted H-transfer process. To better differentiate, we term these processes as ‘Formal Reductive Hydrogen Transfer’ (FRHT) for TS1 and ‘Formal Oxidative Hydrogen Transfer’ (FOHT) for TS2.

  1. Quantum Monte Carlo simulation


    Wang, Yazhen


    Contemporary scientific studies often rely on the understanding of complex quantum systems via computer simulation. This paper initiates the statistical study of quantum simulation and proposes a Monte Carlo method for estimating analytically intractable quantities. We derive the bias and variance for the proposed Monte Carlo quantum simulation estimator and establish the asymptotic theory for the estimator. The theory is used to design a computational scheme for minimizing the mean square er...

  2. Monte Carlo transition probabilities


    Lucy, L. B.


    Transition probabilities governing the interaction of energy packets and matter are derived that allow Monte Carlo NLTE transfer codes to be constructed without simplifying the treatment of line formation. These probabilities are such that the Monte Carlo calculation asymptotically recovers the local emissivity of a gas in statistical equilibrium. Numerical experiments with one-point statistical equilibrium problems for Fe II and Hydrogen confirm this asymptotic behaviour. In addition, the re...

  3. Bond diluted Ising model in 2D

    Directory of Open Access Journals (Sweden)

    Bouamrane Rachid


    Full Text Available The bond diluted Ising model is studied by Monte Carlo method. The simulation is carried out on a two dimensional square lattice with missing bonds and free boundary conditions. The aim of this work is to investigate the thermodynamical properties of this model for different disorder degree parameter σ. The critical temperature is determined from the Binder cumulant and is shown to decreases as the disorder parameter σ increases linearly.

  4. a-C(:H) and a-C(:H){sub Z}r coatings deposited on biomedical Ti-based substrates: Tribological properties

    Energy Technology Data Exchange (ETDEWEB)

    Escudeiro, A., E-mail: [SEG-CEMUC, Department of Mechanical Engineering, University of Coimbra, 3030-788 Coimbra (Portugal); Polcar, T. [National Centre for Advanced Tribology (nCATS), School of Engineering Sciences, University of Southampton, Highfield, Southampton, SO17 1BJ (United Kingdom); Department of Control Engineering, Czech Technical University in Prague, Technicka 2, Prague 6 (Czech Republic); Cavaleiro, A. [SEG-CEMUC, Department of Mechanical Engineering, University of Coimbra, 3030-788 Coimbra (Portugal)


    Amorphous carbon (a-C) based coatings are possible candidates as a surface treatment for various biocompatible materials used in medicine. In this study, the carbon coatings co-sputtered with Zr, deposited by dc unbalanced magnetron sputtering in Ar (non-hydrogenated, i.e. a-C/Zr) and Ar + CH{sub 4} (hydrogenated, i.e. a-C:H/Zr) discharges, were investigated and compared with pure carbon films. Polished pure commercial Ti grade 2 and Ti grade 5 ELI (Ti6Al4V) discs were used as substrates. To improve the coating/substrate adhesion, a gradient Ti-based interlayer was deposited (∼ 450 nm). The coating structure was characterized by X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy; the chemical composition was measured by electron probe microanalysis. The adhesion was evaluated by scratch-test and the hardness was measured by nanoindentation. Tribological testing of the coatings was carried out using unidirectional pin-on-disc experiments; pure titanium balls were used as counterparts. The wear rate of the coatings was negligible except for the films with the highest Zr content deposited on Ti grade 2 substrates. - Highlights: ► The incorporation of Zr led to formation of nanocrystalline ZrC embedded into C-matrix. ► a-C:(H)-Zr coatings significantly improved the wear resistance of Ti-based alloys. ► Substrate plastic deformation led to lower coating adhesion on Ti grade 2.

  5. Mechanistic Insights into C-H Oxidations by Ruthenium(III)-Pterin Complexes: Impact of Basicity of the Pterin Ligand and Electron Acceptability of the Metal Center on the Transition States. (United States)

    Mitome, Hiroumi; Ishizuka, Tomoya; Kotani, Hiroaki; Shiota, Yoshihito; Yoshizawa, Kazunari; Kojima, Takahiko


    A ruthenium(II) complex, [Ru(dmdmp)Cl(MeBPA)] (2) (Hdmdmp = N,N-dimethyl-6,7-dimethylpterin, MeBPA = N-methyl-N,N-bis(pyridylmethyl)amine), having a pterin derivative as a proton-accepting ligand, was synthesized and characterized. Complex 2 shows higher basicity than that of a previously reported Ru(II)-pterin complex, [Ru(dmdmp) (TPA)](+) (1) (TPA = tris(2-pyridylmethyl)amine). On the other hand, 1e(-)-oxidized species of 1 (1OX) exhibits higher electron-acceptability than that of 1e(-)-oxidized 2 (2OX). Bond dissociation enthalpies (BDE) of the two Ru(II) complexes having Hdmdmp as a ligand in proton-coupled electron transfer (PCET) to generate 1OX and 2OX were calculated to be 85 kcal mol(-1) for 1OX and 78 kcal mol(-1) for 2OX. The BDE values are large enough to perform H atom transfer from C-H bonds of organic molecules to the 1e(-)-oxidized complexes through PCET. The second-order rate constants (k) of PCET oxidation reactions were determined for 1OX and 2OX. The logarithms of normalized k values were proportional to the BDE values of C-H bonds of the substrates with slopes of -0.27 for 1OX and -0.44 for 2OX. The difference between 1OX and 2OX in the slopes suggests that the transition states in PCET oxidations of substrates by the two complexes bear different polarization, as reflection of difference in the electron acceptability and basicity of 1OX and 2OX. The more basic 2OX attracts a proton from a C-H bond via a more polarized transition state than that of 1OX; on the contrary, the more electron-deficient 1OX forms less polarized transition states in PCET oxidation reactions of C-H bonds.

  6. A Transcultural Perspective: Reaction to C.H. Patterson's "Multicultural Counseling: From Diversity to Universality." (United States)

    McFadden, John


    Reacts to C. H. Patterson's article (this issue) concerning multicultural counseling. Suggestion that all counseling is generic in nature contributes to the retardation of the developmental process of culturally diverse persons. Supports the notion that cultural competence is imperative in resolving the challenge of counseling with members of…

  7. Tribological behavior and thermal stability of TiC/a-C : H nanocomposite coatings

    NARCIS (Netherlands)

    Pei, Y.T.; Galvan, D.; Hosson, J.Th.M. De


    Advanced TiC/a-C:H nanocomposite coatings have been produced via reactive deposition in a closed-field unbalanced magnetron sputtering system (Hauzer HTC-1200). These wear-resistant coatings are targeted for automotive applications where high load-bearing capacity and thermal stability, low friction

  8. Whole-​cell biocatalysts for stereoselective C-H amination reactions

    NARCIS (Netherlands)

    Both, P.; Busch, H.; Kelly, P.P.; Mutti, F.G.; Turner, N.J.; Flitsch, S.L.


    Enantiomerically pure chiral amines are ubiquitous chemical building blocks in bioactive pharmaceutical products and their synthesis from simple starting materials is of great interest. One of the most attractive strategies is the stereoselective installation of a chiral amine through C H amination,

  9. Cobalt-catalyzed C-H olefination of aromatics with unactivated alkenes. (United States)

    Manoharan, Ramasamy; Sivakumar, Ganesan; Jeganmohan, Masilamani


    A cobalt-catalyzed C-H olefination of aromatic and heteroaromatic amides with unactivated alkenes, allyl acetates and allyl alcohols is described. This method offers an efficient route for the synthesis of vinyl and allyl benzamides in a highly stereoselective manner. It is observed that the ortho substituent on the benzamide moiety is crucial for the observation of allylated products in unactivated alkenes.

  10. Type-studies in the Polyporaceae—I. Tropical species described by C. H. Persoon

    NARCIS (Netherlands)

    Ryvarden, Leif


    The type specimens of 20 tropical polypores described by C. H. Persoon have been examined. Eleven species are accepted, seven are reduced to synonymy, while one name is a nomen nudum. One type is so poorly developed that no conclusive determination is possible. The combination Trametes marianna

  11. Nanostructure and properties of TiC/a-C : H composite coatings

    NARCIS (Netherlands)

    Pei, Y.T.; Galvan, D.; Hosson, J.Th.M. De


    TiC/a-C:H nanocomposite coatings, deposited with closed-field unbalanced magnetron sputtering, have been scrutinized with atomic force, scanning and high-resolution transmission electron microscopy, nanoindentation and tribo-tests. These coatings consist of 2-5 nm TiC nanocrystallites embedded in an

  12. On the composition analysis of nc-TiC/a-C : H nanocomposite coatings

    NARCIS (Netherlands)

    Chechenin, N.G.; Chernykh, P.N.; Kulikauskas, V.S.; Pei, Y.T.; Vainshtein, D.; Hosson, J.Th.M. De


    Using a set of ion beam analysis (IBA) techniques the compositions of hydrogenated diamond-like carbon (DLC) nanocomposite coatings are scrutinized, including the hydrogen content. The coatings are composed of two constituents: amorphous hydrocarbon matrix (a-C : H) and nanocrystalline titanium carb

  13. Preparation and comparison of a-C:H coatings using reactive sputter techniques

    Energy Technology Data Exchange (ETDEWEB)

    Keunecke, M., E-mail: martin.keunecke@ist.fraunhofer.d [Fraunhofer Institute for Surface Engineering and Thin Films (IST), Braunschweig (Germany); Weigel, K.; Bewilogua, K. [Fraunhofer Institute for Surface Engineering and Thin Films (IST), Braunschweig (Germany); Cremer, R.; Fuss, H.-G. [CemeCon AG, Wuerselen (Germany)


    Amorphous hydrogenated carbon (a-C:H) coatings are widely used in several industrial applications. These coatings commonly will be prepared by plasma activated chemical vapor deposition (PACVD). The main method used to prepare a-C:H coating in industrial scale is based on a glow discharge in a hydrocarbon gas like acetylene or methane using a substrate electrode powered with medium frequency (m.f. - some 10 to 300 kHz). Some aims of further development are adhesion improvement, increase of hardness and high coating quality on complex geometries. A relatively new and promising technique to fulfil these requirements is the deposition of a-C:H coatings by a reactive d.c. magnetron sputter deposition from a graphite target with acetylene as reactive gas. An advancement of this technique is the deposition in a pulsed magnetron sputter process. Using these three mentioned techniques a-C:H coatings were prepared in the same deposition machine. For adhesion improvement different interlayer systems were applied. The effect of different substrate bias voltages (d.c. and d.c. pulse) was investigated. By applying the magnetron sputter technique in the d.c. pulse mode, plastic hardness values up to 40 GPa could be reached. Besides hardness other mechanical properties like resistance against abrasive wear were measured and compared. Cross sectional SEM images showed the growth structure of the coatings.

  14. Rhodium(III)-Catalyzed C-H Activation Mediated Synthesis of Isoquinolones from Amides and Cyclopropenes. (United States)

    Hyster, Todd K; Rovis, Tomislav


    We have developed a synthesis of 4-substituted isoquinolones from the Rh(III)-catalyzed, C-H activation mediated, coupling of O-pivaloyl benzhydroxamic acids and 3,3-disubstituted cyclopropenes. Experiments suggest the formation of a [4.1.0] bicyclic-system, which can open under acidic conditions to generate the desired isoquinolone.

  15. Bond Boom

    Institute of Scientific and Technical Information of China (English)


    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  16. Bond Boom

    Institute of Scientific and Technical Information of China (English)


    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  17. C+/H2 gas in star-forming clouds and galaxies (United States)

    Nordon, Raanan; Sternberg, Amiel


    We present analytic theory for the total column density of singly ionized carbon (C+) in the optically thick photon dominated regions (PDRs) of far-UV irradiated (star-forming) molecular clouds. We derive a simple formula for the C+ column as a function of the cloud (hydrogen) density, the far-UV field intensity, and metallicity, encompassing the wide range of galaxy conditions. When assuming the typical relation between UV and density in the cold neutral medium, the C+ column becomes a function of the metallicity alone. We verify our analysis with detailed numerical PDR models. For optically thick gas, most of the C+ column is mixed with hydrogen that is primarily molecular (H2), and this `C+/H2' gas layer accounts for almost all of the `CO-dark' molecular gas in PDRs. The C+/H2 column density is limited by dust shielding and is inversely proportional to the metallicity down to ˜0.1 solar. At lower metallicities, H2 line blocking dominates and the C+/H2 column saturates. Applying our theory to CO surveys in low-redshift spirals, we estimate the fraction of C+/H2 gas out of the total molecular gas to be typically ˜0.4. At redshifts 1 < z < 3 in massive disc galaxies the C+/H2 gas represents a very small fraction of the total molecular gas (≲ 0.16). This small fraction at high redshifts is due to the high gas surface densities when compared to local galaxies.

  18. Red- and blue-shifted hydrogen bonds in the cis-trans noncyclic formic acid dimer. (United States)

    Zhou, Pan-Pan; Qiu, Wen-Yuan


    The cis-trans noncyclic formic acid dimer was studied by means of MP2 method with 6-31G(d,p), 6-31+G(d,p) and 6-311+G(d,p) basis sets. It exhibits simultaneously red-shifted O-H...O and blue-shifted C-H...O hydrogen bonds. AIM and NBO analyses are performed at the MP2/6-31+G(d,p) level to explore their properties and origins. AIM analysis provides the evidence that the O-H bond becomes weaker and the C-H bond becomes stronger upon the hydrogen bond formations. Intermolecular and intramolecular hyperconjugations have important influence on the electron densities in the X-H (X = O, C) sigma bonding orbital and its sigma* antibonding orbital. The electron densities in the two orbitals are closely connected with the X-H (X = O, C) bond length, and they are used to quantitatively estimate the bond length variation. The larger amount of charge transfer in the red-shifted O-H...O hydrogen bond is due to its favorable H...O electron channel, whereas the H...O electron channel in the blue-shifted C-H...O hydrogen bond is weaker. Structural reorganization effects shorten the C-H bond by approximately 30% when compared to the C-H bond contraction upon the dimerization. Strikingly, it leads to a small elongation and a slight red shift of the O-H bond. Both rehybridization and repolarization result in the X-H (X = O, C) bond contraction, but their effects on the O-H bond do not hold a dominant position. The hydrogen-bonding processes go through the electrostatic attractions, van der Waals interactions, charge-transfer interactions, hydrogen-bonding interactions and electrostatic repulsions. Electrostatic attractions are of great importance on the origin of the red-shifted O-H...O hydrogen bond, especially the strong H(delta+)...O(delta-) attraction. For the blue-shifted C-H...O hydrogen bond, the considerable nucleus-nucleus repulsion between H and O atoms caused by the strong electrostatic attraction between C and O atoms is a possible reason for the C-H bond contraction and

  19. Asymmetric nitrene transfer reactions: sulfimidation, aziridination and C-H amination using azide compounds as nitrene precursors. (United States)

    Uchida, Tatsuya; Katsuki, Tsutomu


    Nitrogen functional groups are found in many biologically active compounds and their stereochemistry has a profound effect on biological activity. Nitrene transfer reactions such as aziridination, C-H bond amination, and sulfimidation are useful methods for introducing nitrogen functional groups, and the enantiocontrol of the reactions has been extensively investigated. Although high enantioselectivity has been achieved, most of the reactions use (N-arylsulfonylimino)phenyliodinane, which co-produces iodobenzene, as a nitrene precursor and have a low atom economy. Azide compounds, which give nitrene species by releasing nitrogen, are ideal precursors but rather stable. Their decomposition needs UV irradiation, heating in the presence of a metal complex, or Lewis acid treatment. The examples of previous azide decomposition prompted us to examine Lewis acid and low-valent transition-metal complexes as catalysts for azide decomposition. Thus, we designed new ruthenium complexes that are composed of a low-valent Ru(II) ion, apical CO ligand, and an asymmetry-inducing salen ligand. With these ruthenium complexes and azides, we have achieved highly enantioselective nitrene transfer reactions under mild conditions. Recently, iridium-salen complexes were added to our toolbox. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Axial Ligand Coordination to the C-H Amination Catalyst Rh2(esp)2: A Structural and Spectroscopic Study. (United States)

    Warzecha, Evan; Berto, Timothy C; Berry, John F


    The compound Rh2(esp)2 (esp = α,α,α',α'-tetramethyl-1,3-benzenediproponoate) is the most generally effective catalyst for nitrenoid amination of C-H bonds. However, much of its fundamental coordination chemistry is unknown. In this work, we study the effects of axial ligand coordination to the catalyst Rh2(esp)2. We report here crystal structures, cyclic voltammetry, UV-vis, IR, Raman, and (1)H NMR spectra for the complexes Rh2(esp)2L2 where L = pyridine, 3-picoline, 2,6-lutidine, acetonitrile, and methanol. The compounds all show well-defined π* → σ* electronic transitions in the 16500 to 20500 cm(-1) range, and Rh-Rh stretching vibrations in the range from 304 to 322 cm(-1). Taking these data into account we find that the strength of axial ligand binding to Rh2(esp)2 increases in the series CH3OH ∼ 2,6-lutidine < CH3CN < 3-methylpyridine ∼ pyridine. Quasi-reversible Rh2(4+/5+) redox waves are only obtained when either acetonitrile or no axial ligand is present. In the presence of pyridines, irreversible oxidation waves are observed, suggesting that these ligands destabilize the Rh2 complex under oxidative conditions.

  1. CERN honours Carlo Rubbia

    CERN Multimedia


    Carlo Rubbia turned 75 on March 31, and CERN held a symposium to mark his birthday and pay tribute to his impressive contribution to both CERN and science. Carlo Rubbia, 4th from right, together with the speakers at the symposium.On 7 April CERN hosted a celebration marking Carlo Rubbia’s 75th birthday and 25 years since he was awarded the Nobel Prize for Physics. "Today we will celebrate 100 years of Carlo Rubbia" joked CERN’s Director-General, Rolf Heuer in his opening speech, "75 years of his age and 25 years of the Nobel Prize." Rubbia received the Nobel Prize along with Simon van der Meer for contributions to the discovery of the W and Z bosons, carriers of the weak interaction. During the symposium, which was held in the Main Auditorium, several eminent speakers gave lectures on areas of science to which Carlo Rubbia made decisive contributions. Among those who spoke were Michel Spiro, Director of the French National Insti...

  2. Deposition of a-C:H films on a nanotrench pattern by bipolar PBII&D (United States)

    Hirata, Yuki; Nakahara, Yuya; Nagato, Keisuke; Choi, Junho


    In this study, hydrogenated amorphous carbon (a-C:H) films were deposited on a nanotrench pattern (300 nm pitch, aspect ratio: 2.0) by bipolar-type plasma based ion implantation and deposition technique (bipolar PBII&D), and the effects of bipolar pulse on the film properties were investigated. Moreover, the behaviour of ions and radicals surrounding the nanotrench was analyzed to clarify the coating mechanism and properties of the a-C:H films on the nanotrench. Further, thermal nanoimprint lithography was carried out using the nanotrench pattern coated with a-C:H films as the mold, and the mold release properties were evaluated. All nanotrench surfaces were successfully coated with the a-C:H films, but the film thickness on the top, sidewall, and bottom surfaces of the trench were not uniform. The surface roughness of the a-C:H films was found to decrease at a higher positive voltage; this happens due to the higher electron temperature around the nanotrench because of the surface migration of plasma particles arrived on the trench. The effects of the negative voltage on the behaviour of ions and radicals near the sidewall of the nanotrench are quite similar to those near the microtrench reported previously (Park et al 2014 J. Phys. D: Appl. Phys. 47 335306). However, the positive pulse voltage was also found to affect the behaviour of ions and radicals near the sidewall surface. The incident angles of ions on the sidewall surface increased with the positive pulse voltage because the energy of incoming ions on the trench decreases with increasing positive voltage. Moreover, the incident ion flux on the sidewall is affected by the positive voltage history. Further, the radical flux decreases with increasing positive voltage. It can be concluded that a higher positive voltage at a lower negative voltage condition is good to obtain better film properties and higher film thickness on the sidewall surface. Pattern transfer properties for the nanoimprint formed by

  3. The Virtual Monte Carlo

    CERN Document Server

    Hrivnacova, I; Berejnov, V V; Brun, R; Carminati, F; Fassò, A; Futo, E; Gheata, A; Caballero, I G; Morsch, Andreas


    The concept of Virtual Monte Carlo (VMC) has been developed by the ALICE Software Project to allow different Monte Carlo simulation programs to run without changing the user code, such as the geometry definition, the detector response simulation or input and output formats. Recently, the VMC classes have been integrated into the ROOT framework, and the other relevant packages have been separated from the AliRoot framework and can be used individually by any other HEP project. The general concept of the VMC and its set of base classes provided in ROOT will be presented. Existing implementations for Geant3, Geant4 and FLUKA and simple examples of usage will be described.

  4. Top Quark Flavor Changing Decay t → cH0 in Little Higgs Model

    Institute of Scientific and Technical Information of China (English)

    Farshid Tabbakh; LIU Jing-Jing; MA Wen-Gan; ZHANG Ren-You; HOU Hong-Sheng


    We study theoretically the quantum effects of the littlest Higgs model (LH) mediated by flavor changing one-loop Feynman diagrams on the rare decay process t → cH0. The comparison of the decay width in the LH model with that in the standard model (SM) is made. We find that the decay branch ratio of t → cH0 in the LH model is at most of the order ~ 10-12, which is two order larger than in the SM. The numerical results show that the difference between the branch ratios in the LH model and the SM is generally sensitive to the LH model parameters, such as symmetry breaking scale f, Higgs boson mass mH0, and x = v'4f /v2 in our chosen parameter space, but relatively insensitive to the value choice of the cosine of the mixing angle c and the ratio λ1/λ2.

  5. Charge Transport Properties of Tetrabenz[a,c,h,jl-anthracene Derivatives

    Institute of Scientific and Technical Information of China (English)

    CHEN Zi-Ran; YU Wen-Hao; LI Quan


    Charge transport properties of F, OH, OCH3, SH and SCH3-substituted tetra- benz[a,c,h,j]- anthracene derivative molecules have been investigated theoretically at the B3LYP/6-31G** level using Marcus theory. The results showed that at 300 K, the hole or electron transport capability of F or SH-substituted molecules was better obviously than that of OH or OCH3-substituted molecules, The electron transport capability of SCH3-substituted and F or SH-substituted molecules was superior to their hole transport capability, respectively. F, SH or SCH3-substituted tetrabenz[a,c,h,j]-anthracene derivative molecules can be used as electron transport materials.

  6. Platinum containing amorphous hydrogenated carbon (a-C:H/Pt) thin films as selective solar absorbers

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Yung-Hsiang; Brahma, Sanjaya [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan (China); Tzeng, Y.H. [Department of Electrical Engineering, National Cheng Kung University, Tainan 701, Taiwan (China); Ting, Jyh-Ming, E-mail: [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan (China); Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan 701, Taiwan (China)


    We have investigated a double-cermet structured thin film in which an a-C:H thin film was used as an anti-reflective (AR) layer and two platinum-containing amorphous hydrogenated carbon (a-C:H/Pt) thin films were used as the double cermet layers. A reactive co-sputter deposition method was used to prepare both the anti-reflective and cermet layers. Effects of the target power and heat treatment were studied. The obtained films were characterized using X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy. The optical absorptance and emittance of the as deposited and annealed films were determined using UV–vis-NIR spectroscopy. We show that the optical absorptance of the resulting double-cermet structured thin film is as high as 96% and remains to be 91% after heat treatment at 400 °C, indicating the thermal stability of the film.

  7. C-H amination in the synthesis of N-heterocycles


    Fu, Hua; Yu,Jipan


    Jipan Yu, Hua Fu Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing, People's Republic of China Abstract: N-heterocycles are important motifs in natural products and pharmaceuticals. Recently, the transition metal–catalyzed C-H amination has become a subject in the synthesis of N-heterocycles because of use of the readily available starting materials, high efficiency, economy,...

  8. Non-Directed Allylic C-H Acetoxylation in the Presence of Lewis Basic Heterocycles. (United States)

    Malik, Hasnain A; Taylor, Buck L H; Kerrigan, John R; Grob, Jonathan E; Houk, K N; Du Bois, J; Hamann, Lawrence G; Patterson, Andrew W


    We outline a strategy to enable non-directed Pd(II)-catalyzed C-H functionalization in the presence of Lewis basic heterocycles. In a high-throughput screen of two Pd-catalyzed C-H acetoxylation reactions, addition of a variety of N-containing heterocycles is found to cause low product conversion. A pyridine-containing test substrate is selected as representative of heterocyclic scaffolds that are hypothesized to cause catalyst arrest. We pursue two approaches in parallel that allow product conversion in this representative system: Lewis acids are found to be effective in situ blocking groups for the Lewis basic site, and a pre-formed pyridine N-oxide is shown to enable high yield of allylic C-H acetoxylation. Computational studies with density functional theory (M06) of binding affinities of selected heterocycles to Pd(OAc)2 provide an inverse correlation of the computed heterocycle-Pd(OAc)2 binding affinities with the experimental conversions to products. Additionally, (1)H NMR binding studies provide experimental support for theoretical calculations.

  9. Carlo Caso (1940 - 2007)

    CERN Multimedia

    Leonardo Rossi

    Carlo Caso (1940 - 2007) Our friend and colleague Carlo Caso passed away on July 7th, after several months of courageous fight against cancer. Carlo spent most of his scientific career at CERN, taking an active part in the experimental programme of the laboratory. His long and fruitful involvement in particle physics started in the sixties, in the Genoa group led by G. Tomasini. He then made several experiments using the CERN liquid hydrogen bubble chambers -first the 2000HBC and later BEBC- to study various facets of the production and decay of meson and baryon resonances. He later made his own group and joined the NA27 Collaboration to exploit the EHS Spectrometer with a rapid cycling bubble chamber as vertex detector. Amongst their many achievements, they were the first to measure, with excellent precision, the lifetime of the charmed D mesons. At the start of the LEP era, Carlo and his group moved to the DELPHI experiment, participating in the construction and running of the HPC electromagnetic c...

  10. Carlos Vesga Duarte


    Pedro Medina Avendaño


    Carlos Vega Duarte tenía la sencillez de los seres elementales y puros. Su corazón era limpio como oro de aluvión. Su trato directo y coloquial ponía de relieve a un santandereano sin contaminaciones que amaba el fulgor de las armas y se encandilaba con el destello de las frases perfectas

  11. Microstructure characterization of advanced protective Cr/CrN+a-C:H/a-C:H:Cr multilayer coatings on carbon fibre composite (CFC). (United States)

    Major, L; Janusz, M; Lackner, J M; Kot, M; Major, B


    Studies of advanced protective chromium-based coatings on the carbon fibre composite (CFC) were performed. Multidisciplinary examinations were carried out comprising: microstructure transmission electron microscopy (TEM, HREM) studies, micromechanical analysis and wear resistance. Coatings were prepared using a magnetron sputtering technique with application of high-purity chromium and carbon (graphite) targets deposited on the CFC substrate. Selection of the CFC for surface modification in respect to irregularities on the surface making the CFC surface more smooth was performed. Deposited coatings consisted of two parts. The inner part was responsible for the residual stress compensation and cracking initiation as well as resistance at elevated temperatures occurring namely during surgical tools sterilization process. The outer part was responsible for wear resistance properties and biocompatibility. Experimental studies revealed that irregularities on the substrate surface had a negative influence on the crystallites growth direction. Chromium implanted into the a-C:H structure reacted with carbon forming the cubic nanocrystal chromium carbides of the Cr23 C6 type. The cracking was initiated at the coating/substrate interface and the energy of brittle cracking was reduced because of the plastic deformation at each Cr interlayer interface. The wear mechanism and cracking process was described in micro- and nanoscale by means of transmission electron microscope studies. Examined materials of coated CFC type would find applications in advanced surgical tools.

  12. The azomethine ylide route to amine C-H functionalization: redox-versions of classic reactions and a pathway to new transformations. (United States)

    Seidel, Daniel


    Conspectus Redox-neutral methods for the functionalization of amine α-C-H bonds are inherently efficient because they avoid external oxidants and reductants and often do not generate unwanted byproducts. However, most of the current methods for amine α-C-H bond functionalization are oxidative in nature. While the most efficient variants utilize atmospheric oxygen as the terminal oxidant, many such transformations require the use of expensive or toxic oxidants, often coupled with the need for transition metal catalysts. Redox-neutral amine α-functionalizations that involve intramolecular hydride transfer steps provide viable alternatives to certain oxidative reactions. These processes have been known for some time and are particularly well suited for tertiary amine substrates. A mechanistically distinct strategy for secondary amines has emerged only recently, despite sharing common features with a range of classic organic transformations. Among those are such widely used reactions as the Strecker, Mannich, Pictet-Spengler, and Kabachnik-Fields reactions, Friedel-Crafts alkylations, and iminium alkynylations. In these classic processes, condensation of a secondary amine with an aldehyde (or a ketone) typically leads to the formation of an intermediate iminium ion, which is subsequently attacked by a nucleophile. The corresponding redox-versions of these transformations utilize identical starting materials but incorporate an isomerization step that enables α-C-H bond functionalization. Intramolecular versions of these reactions include redox-neutral amine α-amination, α-oxygenation, and α-sulfenylation. In all cases, a reductive N-alkylation is effectively combined with an oxidative α-functionalization, generating water as the only byproduct. Reactions are promoted by simple carboxylic acids and in some cases require no additives. Azomethine ylides, dipolar species whose usage is predominantly in [3 + 2] cycloadditions and other pericyclic processes, have been

  13. Overcoming the Limitations of C-H Activation with Strongly Coordinating N-Heterocycles by Cobalt Catalysis. (United States)

    Wang, Hui; Lorion, Mélanie M; Ackermann, Lutz


    Strongly coordinating nitrogen heterocycles, including pyrimidines, oxazolines, pyrazoles, and pyridines, were fully tolerated in cobalt-catalyzed C-H amidations by imidate assistance. Structurally complex quinazolines are thus accessible in a step-economic manner. Our findings also establish the relative powers of directing groups in cobalt(III)-catalyzed C-H functionalization for the first time.

  14. Diarylindenotetracenes via a selective cross-coupling/C-H functionalization: electron donors for organic photovoltaic cells. (United States)

    Gu, Xingxian; Luhman, Wade A; Yagodkin, Elisey; Holmes, Russell J; Douglas, Christopher J


    A direct synthesis of new donor materials for organic photovoltaic cells is reported. Diaryindenotetracenes were synthesized utilizing a Kumada-Tamao-Corriu cross-coupling of peri-substituted tetrachlorotetracene with spontaneous indene annulation via C-H activation. Vacuum deposited planar heterojunction organic photovoltaic cells incorporating these molecules as electron donors exhibit power conversion efficiencies exceeding 1.5% with open-circuit voltages ranging from 0.7 to 1.1 V when coupled with C(60) as an electron acceptor.

  15. Kinetics of Hydrocarbon formation in a-C:H film deposition plasmas

    Energy Technology Data Exchange (ETDEWEB)

    De la Cal, E.; Tabares, F.L.


    The formation of C{sub 2} and C{sub 3} hydrocarbons during the PACVD of a-C-H films from admixtures of methane with H{sub 2} and He has been investigated by mass espectrometry under several deposition condition. The time evolution of the observed species indicates that the formation mechanism of ethylene and acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene are sensitive to the conditions of the wall during the growing of the carburized metal. (Author)

  16. Kinetics of Hydrocarbon formation in a- C:H Film deposition plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Cal, E. de la; Tabares, F. L.


    The formation of C2 and Cp hydrocarbons during the PACVD of a-C:H films from admixtures of methane with H2 and He has been investigated by mass spectrometry under several deposition condition. The time evolution of the observed species indicates that the formation mechanisms of ethylene and acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene formation was found to be directly related to the formation of the film on top of the carburized metal. (Author) 12 refs.

  17. Monte Carlo Option Princing

    Directory of Open Access Journals (Sweden)

    Cecilia Maya


    Full Text Available El método Monte Carlo se aplica a varios casos de valoración de opciones financieras. El método genera una buena aproximación al comparar su precisión con la de otros métodos numéricos. La estimación que produce la versión Cruda de Monte Carlo puede ser aún más exacta si se recurre a metodologías de reducción de la varianza entre las cuales se sugieren la variable antitética y de la variable de control. Sin embargo, dichas metodologías requieren un esfuerzo computacional mayor por lo cual las mismas deben ser evaluadas en términos no sólo de su precisión sino también de su eficiencia.

  18. Monte Carlo and nonlinearities

    CERN Document Server

    Dauchet, Jérémi; Blanco, Stéphane; Caliot, Cyril; Charon, Julien; Coustet, Christophe; Hafi, Mouna El; Eymet, Vincent; Farges, Olivier; Forest, Vincent; Fournier, Richard; Galtier, Mathieu; Gautrais, Jacques; Khuong, Anaïs; Pelissier, Lionel; Piaud, Benjamin; Roger, Maxime; Terrée, Guillaume; Weitz, Sebastian


    The Monte Carlo method is widely used to numerically predict systems behaviour. However, its powerful incremental design assumes a strong premise which has severely limited application so far: the estimation process must combine linearly over dimensions. Here we show that this premise can be alleviated by projecting nonlinearities on a polynomial basis and increasing the configuration-space dimension. Considering phytoplankton growth in light-limited environments, radiative transfer in planetary atmospheres, electromagnetic scattering by particles and concentrated-solar-power-plant productions, we prove the real world usability of this advance on four test-cases that were so far regarded as impracticable by Monte Carlo approaches. We also illustrate an outstanding feature of our method when applied to sharp problems with interacting particles: handling rare events is now straightforward. Overall, our extension preserves the features that made the method popular: addressing nonlinearities does not compromise o...

  19. Fundamentals of Monte Carlo

    Energy Technology Data Exchange (ETDEWEB)

    Wollaber, Allan Benton [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    This is a powerpoint presentation which serves as lecture material for the Parallel Computing summer school. It goes over the fundamentals of the Monte Carlo calculation method. The material is presented according to the following outline: Introduction (background, a simple example: estimating π), Why does this even work? (The Law of Large Numbers, The Central Limit Theorem), How to sample (inverse transform sampling, rejection), and An example from particle transport.

  20. Carlos Vesga Duarte

    Directory of Open Access Journals (Sweden)

    Pedro Medina Avendaño


    Full Text Available Carlos Vega Duarte tenía la sencillez de los seres elementales y puros. Su corazón era limpio como oro de aluvión. Su trato directo y coloquial ponía de relieve a un santandereano sin contaminaciones que amaba el fulgor de las armas y se encandilaba con el destello de las frases perfectas

  1. The methyl C-H blueshift in N,N-dimethylformamide-water mixtures probed by two-dimensional Fourier-transform infrared spectroscopy. (United States)

    Xu, Zheng; Li, Haoran; Wang, Congmin; Pan, Haihua; Han, Shijun


    Two-dimensional correlation spectroscopy was used to study the composition-dependent spectral variations of the CH-stretching bands of N,N-dimethylformamide (DMF)-water mixtures with X(DMF) ranging from 0.98 to 0.60. By a detailed correlation analysis of the spectral changes of the CH- and OH-stretching bands, it is found that the intensities of the CH and OH bands change in different ways when the water content is increased. It is also found that two different regions of the water content can be distinguished, in which the intensity changes have different signatures. A tentative explanation for how these phenomena might be related to structural changes in the mixture is proposed. The structural change of DMF induced by the water hydrogen bonded on the carbonyl group is supposed to be the possible origin of the methyl C-H blueshift instead of the direct C-H...O interactions before the hydrophobic hydration takes place.

  2. Mechanistic Insight into the Intramolecular Benzylic C-H Nitrene Insertion Catalyzed by Bimetallic Paddlewheel Complexes: Influence of the Metal Centers. (United States)

    Zhang, Xuepeng; Xu, Huiying; Liu, Xueping; Phillips, David Lee; Zhao, Cunyuan


    The intramolecular benzylic C-H amination catalyzed by bimetallic paddlewheel complexes was investigated by using density functional theory calculations. The metal-metal bonding characters were investigated and the structures featuring either a small HOMO-LUMO gap or a compact SOMO energy scope were estimated to facilitate an easier one-electron oxidation of the bimetallic center. The hydrogen-abstraction step was found to occur through three manners, that is, hydride transfer, hydrogen migration, and proton transfer. The imido N species are more preferred in the Ru-Ru and Pd-Mn cases whereas coexisting N species, namely, singlet/triplet nitrene and imido, were observed in the Rh-Rh and Pd-Co cases. On the other hand, the triplet nitrene N species were found to be predominant in the Pd-Ni and Pd-Zn systems. A concerted asynchronous mechanism was found to be modestly favorable in the Rh-Rh-catalyzed reactions whereas the Pd-Co-catalyzed reactions demonstrated a slight preference for a stepwise pathway. Favored stepwise pathways were seen in each Ru-Ru- and Pd-Mn-catalyzed reactions and in the triplet nitrene involved Pd-Ni and Pd-Zn reactions. The calculations suggest the feasibility of the Pd-Mn, Pd-Co, and Pd-Ni paddlewheel complexes as being economical alternatives for the expensive dirhodium/diruthenium complexes in C-H amination catalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Sub-micro a-C:H patterning of silicon surfaces assisted by atmospheric-pressure plasma-enhanced chemical vapor deposition (United States)

    Boileau, Alexis; Gries, Thomas; Noël, Cédric; Perito Cardoso, Rodrigo; Belmonte, Thierry


    Micro and nano-patterning of surfaces is an increasingly popular challenge in the field of the miniaturization of devices assembled via top-down approaches. This study demonstrates the possibility of depositing sub-micrometric localized coatings—spots, lines or even more complex shapes—made of amorphous hydrogenated carbon (a-C:H) thanks to a moving XY stage. Deposition was performed on silicon substrates using chemical vapor deposition assisted by an argon atmospheric-pressure plasma jet. Acetylene was injected into the post-discharge region as a precursor by means of a glass capillary with a sub-micrometric diameter. A parametric study was carried out to study the influence of the geometric configurations (capillary diameter and capillary-plasma distance) on the deposited coating. Thus, the patterns formed were investigated by scanning electron microscopy and atomic force microscopy. Furthermore, the chemical composition of large coated areas was investigated by Fourier transform infrared spectroscopy according to the chosen atmospheric environment. The observed chemical bonds show that reactions of the gaseous precursor in the discharge region and both chemical and morphological stability of the patterns after treatment are strongly dependent on the surrounding gas. Various sub-micrometric a-C:H shapes were successfully deposited under controlled atmospheric conditions using argon as inerting gas. Overall, this new process of micro-scale additive manufacturing by atmospheric plasma offers unusually high-resolution at low cost.

  4. Who Writes Carlos Bulosan?

    Directory of Open Access Journals (Sweden)

    Charlie Samuya Veric


    Full Text Available The importance of Carlos Bulosan in Filipino and Filipino-American radical history and literature is indisputable. His eminence spans the pacific, and he is known, diversely, as a radical poet, fictionist, novelist, and labor organizer. Author of the canonical America Iis the Hearts, Bulosan is celebrated for chronicling the conditions in America in his time, such as racism and unemployment. In the history of criticism on Bulosan's life and work, however, there is an undeclared general consensus that views Bulosan and his work as coherent permanent texts of radicalism and anti-imperialism. Central to the existence of such a tradition of critical reception are the generations of critics who, in more ways than one, control the discourse on and of Carlos Bulosan. This essay inquires into the sphere of the critical reception that orders, for our time and for the time ahead, the reading and interpretation of Bulosan. What eye and seeing, the essay asks, determine the perception of Bulosan as the angel of radicalism? What is obscured in constructing Bulosan as an immutable figure of the political? What light does the reader conceive when the personal is brought into the open and situated against the political? the essay explores the answers to these questions in Bulosan's loving letters to various friends, strangers, and white American women. The presence of these interrogations, the essay believes, will secure ultimately the continuing importance of Carlos Bulosan to radical literature and history.

  5. CERN honours Carlo Rubbia

    CERN Multimedia


    On 7 April CERN will be holding a symposium to mark the 75th birthday of Carlo Rubbia, who shared the 1984 Nobel Prize for Physics with Simon van der Meer for contributions to the discovery of the W and Z bosons, carriers of the weak interaction. Following a presentation by Rolf Heuer, lectures will be given by eminent speakers on areas of science to which Carlo Rubbia has made decisive contributions. Michel Spiro, Director of the French National Institute of Nuclear and Particle Physics (IN2P3) of the CNRS, Lyn Evans, sLHC Project Leader, and Alan Astbury of the TRIUMF Laboratory will talk about the physics of the weak interaction and the discovery of the W and Z bosons. Former CERN Director-General Herwig Schopper will lecture on CERN’s accelerators from LEP to the LHC. Giovanni Bignami, former President of the Italian Space Agency and Professor at the IUSS School for Advanced Studies in Pavia will speak about his work with Carlo Rubbia. Finally, Hans Joachim Sch...

  6. CERN honours Carlo Rubbia

    CERN Multimedia


    On 7 April CERN will be holding a symposium to mark the 75th birthday of Carlo Rubbia, who shared the 1984 Nobel Prize for Physics with Simon van der Meer for contributions to the discovery of the W and Z bosons, carriers of the weak interaction. Following a presentation by Rolf Heuer, lectures will be given by eminent speakers on areas of science to which Carlo Rubbia has made decisive contributions. Michel Spiro, Director of the French National Institute of Nuclear and Particle Physics (IN2P3) of the CNRS, Lyn Evans, sLHC Project Leader, and Alan Astbury of the TRIUMF Laboratory will talk about the physics of the weak interaction and the discovery of the W and Z bosons. Former CERN Director-General Herwig Schopper will lecture on CERN’s accelerators from LEP to the LHC. Giovanni Bignami, former President of the Italian Space Agency, will speak about his work with Carlo Rubbia. Finally, Hans Joachim Schellnhuber of the Potsdam Institute for Climate Research and Sven Kul...

  7. Two lanthanum(III) complexes containing η2-pyrazolate and η2-1,2,4-triazolate ligands: intramolecular C-H...N/O interactions and coordination geometries. (United States)

    Wang, Yu-Long; Feng, Meng; Tao, Xian; Tang, Qing-Yun; Shen, Ying-Zhong


    The lanthanum(III) complexes tris(3,5-diphenylpyrazolato-κ(2)N,N')tris(tetrahydrofuran-κO)lanthanum(III) tetrahydrofuran monosolvate, [La(C(15)H(11)N(2))(3)(C(4)H(8)O)(3)]·C(4)H(8)O, (I), and tris(3,5-diphenyl-1,2,4-triazolato-κ(2)N(1),N(2))tris(tetrahydrofuran-κO)lanthanum(III), [La(C(14)H(10)N(3))(3)(C(4)H(8)O)(3)], (II), both contain La(III) atoms coordinated by three heterocyclic ligands and three tetrahydrofuran ligands, but their coordination geometries differ. Complex (I) has a mer-distorted octahedral geometry, while complex (II) has a fac-distorted configuration. The difference in the coordination geometries and the existence of asymmetric La-N bonding in the two complexes is associated with intramolecular C-H...N/O interactions between the ligands.

  8. Heterogeneously porous γ-MnO₂-catalyzed direct oxidative amination of benzoxazole through C-H activation in the presence of O₂. (United States)

    Pal, Provas; Giri, Arnab Kanti; Singh, Harshvardhan; Ghosh, Subhash Chandra; Panda, Asit Baran


    Oxidative amination of azoles through catalytic C-H bond activation is a very important reaction due to the presence of 2-aminoazoles in several biologically active compounds. However, most of the reported methods are performed under homogeneous reaction conditions using excess reagents and additives. Herein, we report the heterogeneous, porous γ-MnO2-catalyzed direct amination of benzoxazole with wide range of primary and secondary amines. The amination was carried under mild reaction conditions and using molecular oxygen as a green oxidant, without any additives. The catalyst can easily be separated by filtration and reused several times without a significant loss of its catalytic performance. Of note, the reaction tolerates a functional group such as alcohol, thus indicating the broad applicability of this reaction.

  9. The Effect of Thermal Annealing on the Optical Properties of a-SiC:H Films Produced by DC Sputtering Methods: I

    Directory of Open Access Journals (Sweden)

    Lusitra Munisa


    Full Text Available Silicon Target Case. The effects of thermal annealing treatment on the optical properties of amorphous silicon carbon films deposited by silicon target in an argon, methane and hydrogen gas mixture have been studied using ultra violet-visible (uv-vis spectroscopy. Both n and α, and consequently the real and imaginary parts of the dielectric constant, show a considerable variation with subsequent annealing up to annealing temperature 500 °C, with the most rapid changes occurring for temperature 300 °C. The films tend denser as the annealing temperature increased up to 500°C. The optical gap improved slightly upon annealing, where as the disorder of the amorphous network reduced. The annealing treatment produces reorganization of the amorphous network since thermal annealing results in dissociation of hydrogenated bonds (Si-H and C-H.

  10. The role of C-H$\\ldots$ interaction in the stabilization of benzene and adamantane clusters

    Indian Academy of Sciences (India)

    R Mahesh Kumar; M Elango; R Parthasarathi; Dolly Vijay; V Subramanian


    In this investigation, a systematic attempt has been made to understand the interaction between adamantane and benzene using both ab initio and density functional theory methods. C-H$\\ldots$ type of interaction between C-H groups of adamantane and cloud of benzene is found as the important attraction for complex formation. The study also reveals that the methylene (-CH2) and methine (-CH) groups of adamantane interact with benzene resulting in different geometrical structures. And it is found that the former complex is stronger than the later. The diamondoid structure of adamantane enables it to interact with a maximum of four benzene molecules, each one along the four faces. The stability of the complex increases with increase in the number of benzene molecules. The energy decomposition analysis of adamantane-benzene complexes using DMA approach shows that the origin of the stability primarily arises from the dispersive interaction. The theory of atoms in molecules (AIM) supports the existence of weak interaction between the two systems. The electrostatic topography features provide clues for the mode of interaction of adamantane with benzene.

  11. C-H Hot Bands in the Near-IR Emission Spectra of Leonids (United States)

    Freund, F. T.; Scoville, J.; Holm, R.; Seelemann, R.; Freund, M. M.


    The reported infrared (IR) emission spectra from 1999 Leonid fireballs show a 3.4 micron C-H emission band and unidentified bands at longer wavelengths. Upon atmospheric entry, the Leonid meteorites were flash-heated to temperatures around 2400K, which would destroy any organics on the surface of the meteorite grains. We propose that the nu(sub )CH emission band in the Leonid emission spectra arises from matrix-embedded C(sub n)-H-O entities that are protected from instant pyrolysis. Our model is based on IR absorption nu(sub )CH bands, which we observed in laboratory-grown MgO and natural olivine single crystals, where they arise from C(sub n)-H-O units imbedded in the mineral matrix, indicative of aliphatic -CH2- and -CH3 organics. Instead of being pyrolyzed, the C(sub n)-H-O entities in the Leonid trails become vibrationally excited to higher levels n = 1, 2, 3 etc. During de-excitation they emit at 3.4 microns, due to the (0 => 1) transition, and at longer wavelengths, due to hot bands. As a first step toward verifying this hypothesis we measured the C-H vibrational manifold of hexane (C6H14). The calculated positions of the (2 => l ) , (3 => 2), and possibly (4 => 3) hot bands agree with the Leonid emission bands at 3.5, 3.8 and 4.l microns.

  12. Biocompatible Silver-containing a-C:H and a-C coatings: AComparative Study

    Energy Technology Data Exchange (ETDEWEB)

    Endrino, Jose Luis; Allen, Matthew; Escobar Galindo, Ramon; Zhang, Hanshen; Anders, Andre; Albella, Jose Maria


    Hydrogenated diamond-like-carbon (a-C:H) and hydrogen-free amorphous carbon (a-C) coatings are known to be biocompatible and have good chemical inertness. For this reason, both of these materials are strong candidates to be used as a matrix that embeds metallic elements with antimicrobial effect. In this comparative study, we have incorporated silver into diamond-like carbon (DLC) coatings by plasma based ion implantation and deposition (PBII&D) using methane (CH4) plasma and simultaneously depositing Ag from a pulsed cathodic arc source. In addition, we have grown amorphous carbon - silver composite coatings using a dual-cathode pulsed filtered cathodic-arc (FCA) source. The silver atomic content of the deposited samples was analyzed using glow discharge optical spectroscopy (GDOES). In both cases, the arc pulse frequency of the silver cathode was adjusted in order to obtain samples with approximately 5 at.% of Ag. Surface hardness of the deposited films was analyzed using the nanoindentation technique. Cell viability for both a-C:H/Ag and a-C:/Ag samples deposited on 24-well tissue culture plates has been evaluated.

  13. C-H-Activated Direct Arylation of Strong Benzothiadiazole and Quinoxaline-Based Electron Acceptors. (United States)

    Zhang, Junxiang; Parker, Timothy C; Chen, Wayne; Williams, LaRita; Khrustalev, Victor N; Jucov, Evgheni V; Barlow, Stephen; Timofeeva, Tatiana V; Marder, Seth R


    Electron acceptors are important components of π-conjugated materials, but the strong electron-withdrawing properties of the required synthetic intermediates often make them poor substrates in synthetic schemes designed around conventional organometallic cross-coupling. Here, strong benzodiimine-based acceptors, including 5,6-difluoro[2,1,3]benzothiadiazole, 5,6-dicyano[2,1,3]benzothiadiazole, 5,6-dicyanobenzo[d][1,2,3]triazole, 6,7-dicyanoquinoxaline, and 6,7-dinitroquinoxaline, are shown to undergo facile palladium-catalyzed C-H direct arylation with a variety of bromoarenes in moderate to high yields. The electrochemical characteristics of di-2-thienyl derivatives synthesized using this methodology are compared and suggest that, in an electron-transfer sense, 5,6-dicyano[2,1,3]benzothiadiazole is a comparably strong acceptor to benzo[1,2-c:4,5-c']bis[1,2,5]thiadiazole. The synthetic results suggest that high electron-withdrawing ability, which has traditionally limited reaction yields and structural variety in organic electronic materials, may be advantageous when employing C-H activated direct arylation in certain circumstances.

  14. Excess C/O and C/H in outer protoplanetary disk gas

    CERN Document Server

    Oberg, Karin I


    The compositions of nascent planets depend on the compositions of their birth disks. In particular, the elemental compositions of Gas Giant gaseous envelopes depend on the elemental composition of the disk gas from which the envelope is accreted. Previous models demonstrated that sequential freeze-out of O and C-bearing volatiles in disks will result in an supersolar C/O ratios and subsolar C/H ratios in the gas between water and CO snowlines. This result does not take into account, however, the expected grain growth and radial drift of pebbles in disks, and the accompanying re-distribution of volatiles from the outer to the inner disk. Using a toy model we demonstrate that when drift is considered, CO is enhanced between the water and CO snowline, resulting in both supersolar C/O and C/H ratios in the disk gas in the Gas Giant formation zone. This result appears robust to the details of the disk model as long as there is substantial pebble drift across the CO snowline, and the efficiency of CO vapor diffusio...

  15. Novel Stable Compounds in the C-H-O Ternary System at High Pressure (United States)

    Saleh, Gabriele; Oganov, Artem R.


    The chemistry of the elements is heavily altered by high pressure, with stabilization of many new and often unexpected compounds, the emergence of which can profoundly change models of planetary interiors, where high pressure reigns. The C-H-O system is one of the most important planet-forming systems, but its high-pressure chemistry is not well known. Here, using state-of-the-art variable-composition evolutionary searches combined with quantum-mechanical calculations, we explore the C-H-O system at pressures up to 400 GPa. Besides uncovering new stable polymorphs of high-pressure elements and known molecules, we predicted the formation of new compounds. A 2CH4:3H2 inclusion compound forms at low pressure and remains stable up to 215 GPa. Carbonic acid (H2CO3), highly unstable at ambient conditions, was predicted to form exothermically at mild pressure (about 1 GPa). As pressure rises, it polymerizes and, above 314 GPa, reacts with water to form orthocarbonic acid (H4CO4). This unexpected high-pressure chemistry is rationalized by analyzing charge density and electron localization function distributions, and implications for general chemistry and planetary science are also discussed.

  16. Evaluation of the effect of different concentrations of Arsenicum album 6cH on intoxicated rats

    Directory of Open Access Journals (Sweden)

    Cíntia Maria Bertaglia Luizetto


    Full Text Available Aims: Homeopaths diverge on the concept of dose, i.e. the amount of drug that a patient must take to alter his or her state of disease. In order to stimulate reflections on this concept, this study sought to evaluate in vivo the effect of different concentrations of Arsenicum album 6cH prepared according to homeopathic pharmacotechnics. Methods: male Wistar rats were intoxicated with arsenic and then treated with Arsenicum album 6cH and Arsenicum album 6cH diluted at 1%, administered orally. The amount of arsenic retained in the animals’ organism and that eliminated by urine were measured through atomic absorption spectroscopy. Samples of urine were collected before and after intoxication and during treatment. The positive control group (intoxicated animals and the negative control group (non-intoxicated animals received only the vehicle used in the preparation of the medicine. Results: Groups treated with Arsenicum album 6cH and Arsenicum album 6cH diluted at 1% eliminated significant amounts of arsenic when compared to the control groups. The group treated with Arsenicum album 6cH eliminated significantly higher amounts of arsenic than the group treated with the diluted medicine at 1%. Conclusion: results suggest that Arsenicum album 6cH should not be diluted as not to compromise its effectiveness in the treatment of rats intoxicated with arsenic.

  17. On the Importance of C-H/π and C-H⋅⋅⋅H-C Interactions in the Solid State Structure of 15-Lipoxygenase Inhibitors Based on Eugenol Derivatives. (United States)

    Mirzaei, Masoud; Nikpour, Mohsen; Bauzá, Antonio; Frontera, Antonio


    In this manuscript the X-ray structures of two potent and known inhibitors of 15-lipoxygenase, that is, 4-allyl-2-methoxyphenyl-1-admantanecarboxylate (1) and allyl-2-methoxyphenyl-1-cyclohexanecarboxylate (2), are reported. Their solid-state architectures show that they have a strong ability to establish C-H/π and C-H⋅⋅⋅H-C interactions. For the former interaction, the adamantane or cyclohexane moieties are the C-H donors and the electron-rich methoxyphenyl ring is the π system. For the latter, the C-H bonds belong to the aliphatic rings of the inhibitors. Interestingly, the active site of lipoxygenase enzyme family is rich in isoleucine and leucine amino acids that participate in the binding of the unsaturated fatty acid substrate by means of multiple hydrophobic C-H⋅⋅⋅H-C interactions. By means of theoretical calculations, we analyze the ability of compounds 1 and 2 to establish C-H/π and C-H⋅⋅⋅H-C interactions in the solid state.

  18. Study of optimization of Al/a-SiC:H Schottky diodes by means of annealing process of a-SiC:H thin films sputtered at three different hydrogen flow rates

    Directory of Open Access Journals (Sweden)

    L. Magafas


    Full Text Available The aim of the present work is to study the optimization of the electrical and optical properties of a-SiC:H Schottky di-odes using thermal annealing process to a-SiC:H thin films in the range from 300oC up to 675oC. The films were depos-ited onto c-Si(n using the rf sputtered method at three different hydrogen flow rates, 9sccm, 14sccm, and 20sccm. Sub-sequently, Al dots evaporated onto a-SiC:H in order to form Schottky contacts. The measurements of logI-V character-istics have shown that the Al/a-SiC:H Schottky diodes are optimized at 550oC, 575oC, and 600oC , for hydrogen flow rates 9 sccm, 14 sccm and 20 sccm respectively. At these temperatures the logI-V curves are linear for more than seven orders of magnitude, and the majority carries are transported by thermal emission mechanism. The measurements of op-tical response of these diodes present two maximum values (>70%, one in the range from 550nm up to 625nm and the other at 850nm which are attributed to Al/a-SiC:H junction and to a-SiC:H/c-Si(n heterojunction, respectively. From the overall study of the electrical and optical measurements of the Schottky diodes it is concluded that at hydrogen flow rate 20 sccm and annealing temperature 600oC is achieved the optimum Al/a-SiC:H Schottky diode. This result is in full agreement with the properties of the a-SiC:H.

  19. Ing. Carlos M. Ochoa


    Montesinos A, Fernando; Facultad de Farmacia y Bioquímica de la Universidad Nacional Mayor de San Marcos, Lima, Perú.


    Este personaje es un extraordinario investigador dedicado, durante muchos año, al estudio de la papa, tubérculo del genero Solanum y al infinito número de especies y variedades que cubren los territorios del Perú, Bolivia y Chile, y posiblemente otros países. Originalmente silvestre, hoy como resultado del avance científico constituye un alimento de gran valor en el mundo, desde todo punto de vista.Carlos M. Ochoa nació en el Cusco: se trasladó a Bolivia donde llevó a cabo estudios iniciales,...

  20. LMC: Logarithmantic Monte Carlo (United States)

    Mantz, Adam B.


    LMC is a Markov Chain Monte Carlo engine in Python that implements adaptive Metropolis-Hastings and slice sampling, as well as the affine-invariant method of Goodman & Weare, in a flexible framework. It can be used for simple problems, but the main use case is problems where expensive likelihood evaluations are provided by less flexible third-party software, which benefit from parallelization across many nodes at the sampling level. The parallel/adaptive methods use communication through MPI, or alternatively by writing/reading files, and mostly follow the approaches pioneered by CosmoMC (ascl:1106.025).

  1. 2008 C. H. McCloy lecture. Social psychology and physical activity: back to the future. (United States)

    Gill, Diane L


    In the early 1970s, both my academic career and the psychology subdiscipline within kinesiology began as "social psychology and physical activity. "Since then, sport and exercise psychology research has shifted away from the social to a narrower biopsycho-(no social) approach, and professional practice has focused on the elite rather than the larger public. Psychology can contribute to an integrative and relevant professional discipline by going back to the future as social psychology and physical activity and by incorporating three of C. H. McCloy's themes (a) evidence-based practice, (b) beyond dualisms, and (c) commitment to public service. Our scholarship must move beyond dualisms to recognize complexities and connections and be truly scholarship for practice. Social psychology and physical activity can serve the public by advocating for inclusive, empowering physical activity programs that promote health and well being for all.

  2. Copper-promoted methylene C-H oxidation to a ketone derivative by O2

    DEFF Research Database (Denmark)

    Deville, Claire; McKee, Vickie; McKenzie, Christine J.


    ) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO4). The co-ligand in this complex, N-(2′-pyridylcarbonyl)pyridine-2-carboximidate (bpca−), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water...... of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O2. The metastable copper complexes [Cu(dpeo)2](ClO4)2 and [Cu(bpca)(hidpe)](ClO4), along with [NiX2(dpeo)2] (X = Cl, Br), [Ni(dpeo)3](ClO4)2, [Co(dpeo)3](ClO4)3 and the mixed valence complex [FeIIIFeII2(dpeo-H)3(dpeo)3](PF6...

  3. Studies of beauty baryon decays to $D^0 ph^-$ and $\\Lambda_c^+ h^-$ final states

    CERN Document Server

    Aaij, Roel; Adinolfi, Marco; Adrover, Cosme; Affolder, Anthony; Ajaltouni, Ziad; Albrecht, Johannes; Alessio, Federico; Alexander, Michael; Ali, Suvayu; Alkhazov, Georgy; Alvarez Cartelle, Paula; Alves Jr, Antonio; Amato, Sandra; Amerio, Silvia; Amhis, Yasmine; Anderlini, Lucio; Anderson, Jonathan; Andreassen, Rolf; Andreotti, Mirco; Andrews, Jason; Appleby, Robert; Aquines Gutierrez, Osvaldo; Archilli, Flavio; Artamonov, Alexander; Artuso, Marina; Aslanides, Elie; Auriemma, Giulio; Baalouch, Marouen; Bachmann, Sebastian; Back, John; Badalov, Alexey; Balagura, Vladislav; Baldini, Wander; Barlow, Roger; Barschel, Colin; Barsuk, Sergey; Barter, William; Batozskaya, Varvara; Bauer, Thomas; Bay, Aurelio; Beddow, John; Bedeschi, Franco; Bediaga, Ignacio; Belogurov, Sergey; Belous, Konstantin; Belyaev, Ivan; Ben-Haim, Eli; Bencivenni, Giovanni; Benson, Sean; Benton, Jack; Berezhnoy, Alexander; Bernet, Roland; Bettler, Marc-Olivier; van Beuzekom, Martinus; Bien, Alexander; Bifani, Simone; Bird, Thomas; Bizzeti, Andrea; Bjørnstad, Pål Marius; Blake, Thomas; Blanc, Frédéric; Blouw, Johan; Blusk, Steven; Bocci, Valerio; Bondar, Alexander; Bondar, Nikolay; Bonivento, Walter; Borghi, Silvia; Borgia, Alessandra; Bowcock, Themistocles; Bowen, Espen Eie; Bozzi, Concezio; Brambach, Tobias; van den Brand, Johannes; Bressieux, Joël; Brett, David; Britsch, Markward; Britton, Thomas; Brook, Nicholas; Brown, Henry; Bursche, Albert; Busetto, Giovanni; Buytaert, Jan; Cadeddu, Sandro; Calabrese, Roberto; Callot, Olivier; Calvi, Marta; Calvo Gomez, Miriam; Camboni, Alessandro; Campana, Pierluigi; Campora Perez, Daniel; Carbone, Angelo; Carboni, Giovanni; Cardinale, Roberta; Cardini, Alessandro; Carranza-Mejia, Hector; Carson, Laurence; Carvalho Akiba, Kazuyoshi; Casse, Gianluigi; Castillo Garcia, Lucia; Cattaneo, Marco; Cauet, Christophe; Cenci, Riccardo; Charles, Matthew; Charpentier, Philippe; Cheung, Shu-Faye; Chiapolini, Nicola; Chrzaszcz, Marcin; Ciba, Krzystof; Cid Vidal, Xabier; Ciezarek, Gregory; Clarke, Peter; Clemencic, Marco; Cliff, Harry; Closier, Joel; Coca, Cornelia; Coco, Victor; Cogan, Julien; Cogneras, Eric; Collins, Paula; Comerma-Montells, Albert; Contu, Andrea; Cook, Andrew; Coombes, Matthew; Coquereau, Samuel; Corti, Gloria; Couturier, Benjamin; Cowan, Greig; Craik, Daniel Charles; Cruz Torres, Melissa Maria; Cunliffe, Samuel; Currie, Robert; D'Ambrosio, Carmelo; Dalseno, Jeremy; David, Pascal; David, Pieter; Davis, Adam; De Bonis, Isabelle; De Bruyn, Kristof; De Capua, Stefano; De Cian, Michel; De Miranda, Jussara; De Paula, Leandro; De Silva, Weeraddana; De Simone, Patrizia; Decamp, Daniel; Deckenhoff, Mirko; Del Buono, Luigi; Déléage, Nicolas; Derkach, Denis; Deschamps, Olivier; Dettori, Francesco; Di Canto, Angelo; Dijkstra, Hans; Dogaru, Marius; Donleavy, Stephanie; Dordei, Francesca; Dorosz, Piotr; Dosil Suárez, Alvaro; Dossett, David; Dovbnya, Anatoliy; Dupertuis, Frederic; Durante, Paolo; Dzhelyadin, Rustem; Dziurda, Agnieszka; Dzyuba, Alexey; Easo, Sajan; Egede, Ulrik; Egorychev, Victor; Eidelman, Semen; van Eijk, Daan; Eisenhardt, Stephan; Eitschberger, Ulrich; Ekelhof, Robert; Eklund, Lars; El Rifai, Ibrahim; Elsasser, Christian; Falabella, Antonio; Färber, Christian; Farinelli, Chiara; Farry, Stephen; Ferguson, Dianne; Fernandez Albor, Victor; Ferreira Rodrigues, Fernando; Ferro-Luzzi, Massimiliano; Filippov, Sergey; Fiore, Marco; Fiorini, Massimiliano; Fitzpatrick, Conor; Fontana, Marianna; Fontanelli, Flavio; Forty, Roger; Francisco, Oscar; Frank, Markus; Frei, Christoph; Frosini, Maddalena; Furfaro, Emiliano; Gallas Torreira, Abraham; Galli, Domenico; Gandelman, Miriam; Gandini, Paolo; Gao, Yuanning; Garofoli, Justin; Garosi, Paola; Garra Tico, Jordi; Garrido, Lluis; Gaspar, Clara; Gauld, Rhorry; Gersabeck, Evelina; Gersabeck, Marco; Gershon, Timothy; Ghez, Philippe; Gibson, Valerie; Giubega, Lavinia-Helena; Gligorov, V.V.; Göbel, Carla; Golubkov, Dmitry; Golutvin, Andrey; Gomes, Alvaro; Gordon, Hamish; Grabalosa Gándara, Marc; Graciani Diaz, Ricardo; Granado Cardoso, Luis Alberto; Graugés, Eugeni; Graziani, Giacomo; Grecu, Alexandru; Greening, Edward; Gregson, Sam; Griffith, Peter; Grillo, Lucia; Grünberg, Oliver; Gui, Bin; Gushchin, Evgeny; Guz, Yury; Gys, Thierry; Hadjivasiliou, Christos; Haefeli, Guido; Haen, Christophe; Hafkenscheid, Tom; Haines, Susan; Hall, Samuel; Hamilton, Brian; Hampson, Thomas; Hansmann-Menzemer, Stephanie; Harnew, Neville; Harnew, Samuel; Harrison, Jonathan; Hartmann, Thomas; He, Jibo; Head, Timothy; Heijne, Veerle; Hennessy, Karol; Henrard, Pierre; Hernando Morata, Jose Angel; van Herwijnen, Eric; Heß, Miriam; Hicheur, Adlène; Hicks, Emma; Hill, Donal; Hoballah, Mostafa; Hombach, Christoph; Hulsbergen, Wouter; Hunt, Philip; Huse, Torkjell; Hussain, Nazim; Hutchcroft, David; Hynds, Daniel; Iakovenko, Viktor; Idzik, Marek; Ilten, Philip; Jacobsson, Richard; Jaeger, Andreas; Jans, Eddy; Jaton, Pierre; Jawahery, Abolhassan; Jing, Fanfan; John, Malcolm; Johnson, Daniel; Jones, Christopher; Joram, Christian; Jost, Beat; Jurik, Nathan; Kaballo, Michael; Kandybei, Sergii; Kanso, Wallaa; Karacson, Matthias; Karbach, Moritz; Kenyon, Ian; Ketel, Tjeerd; Khanji, Basem; Klaver, Suzanne; Kochebina, Olga; Komarov, Ilya; Koopman, Rose; Koppenburg, Patrick; Korolev, Mikhail; Kozlinskiy, Alexandr; Kravchuk, Leonid; Kreplin, Katharina; Kreps, Michal; Krocker, Georg; Krokovny, Pavel; Kruse, Florian; Kucharczyk, Marcin; Kudryavtsev, Vasily; Kurek, Krzysztof; Kvaratskheliya, Tengiz; La Thi, Viet Nga; Lacarrere, Daniel; Lafferty, George; Lai, Adriano; Lambert, Dean; Lambert, Robert W; Lanciotti, Elisa; Lanfranchi, Gaia; Langenbruch, Christoph; Latham, Thomas; Lazzeroni, Cristina; Le Gac, Renaud; van Leerdam, Jeroen; Lees, Jean-Pierre; Lefèvre, Regis; Leflat, Alexander; Lefrançois, Jacques; Leo, Sabato; Leroy, Olivier; Lesiak, Tadeusz; Leverington, Blake; Li, Yiming; Li Gioi, Luigi; Liles, Myfanwy; Lindner, Rolf; Linn, Christian; Lionetto, Federica; Liu, Bo; Liu, Guoming; Lohn, Stefan; Longstaff, Ian; Lopes, Jose; Lopez-March, Neus; Lu, Haiting; Lucchesi, Donatella; Luisier, Johan; Luo, Haofei; Luppi, Eleonora; Lupton, Oliver; Machefert, Frederic; Machikhiliyan, Irina V; Maciuc, Florin; Maev, Oleg; Malde, Sneha; Manca, Giulia; Mancinelli, Giampiero; Maratas, Jan; Marconi, Umberto; Marino, Pietro; Märki, Raphael; Marks, Jörg; Martellotti, Giuseppe; Martens, Aurelien; Martín Sánchez, Alexandra; Martinelli, Maurizio; Martinez Santos, Diego; Martins Tostes, Danielle; Martynov, Aleksandr; Massafferri, André; Matev, Rosen; Mathe, Zoltan; Matteuzzi, Clara; Maurice, Emilie; Mazurov, Alexander; McCann, Michael; McCarthy, James; McNab, Andrew; McNulty, Ronan; McSkelly, Ben; Meadows, Brian; Meier, Frank; Meissner, Marco; Merk, Marcel; Milanes, Diego Alejandro; Minard, Marie-Noelle; Molina Rodriguez, Josue; Monteil, Stephane; Moran, Dermot; Morawski, Piotr; Mordà, Alessandro; Morello, Michael Joseph; Mountain, Raymond; Mous, Ivan; Muheim, Franz; Müller, Katharina; Muresan, Raluca; Muryn, Bogdan; Muster, Bastien; Naik, Paras; Nakada, Tatsuya; Nandakumar, Raja; Nasteva, Irina; Needham, Matthew; Neubert, Sebastian; Neufeld, Niko; Nguyen, Anh Duc; Nguyen, Thi-Dung; Nguyen-Mau, Chung; Nicol, Michelle; Niess, Valentin; Niet, Ramon; Nikitin, Nikolay; Nikodem, Thomas; Nomerotski, Andrey; Novoselov, Alexey; Oblakowska-Mucha, Agnieszka; Obraztsov, Vladimir; Oggero, Serena; Ogilvy, Stephen; Okhrimenko, Oleksandr; Oldeman, Rudolf; Onderwater, Gerco; Orlandea, Marius; Otalora Goicochea, Juan Martin; Owen, Patrick; Oyanguren, Maria Arantza; Pal, Bilas Kanti; Palano, Antimo; Palutan, Matteo; Panman, Jacob; Papanestis, Antonios; Pappagallo, Marco; Pappalardo, Luciano; Parkes, Christopher; Parkinson, Christopher John; Passaleva, Giovanni; Patel, Girish; Patel, Mitesh; Patrignani, Claudia; Pavel-Nicorescu, Carmen; Pazos Alvarez, Antonio; Pearce, Alex; Pellegrino, Antonio; Penso, Gianni; Pepe Altarelli, Monica; Perazzini, Stefano; Perez Trigo, Eliseo; Pérez-Calero Yzquierdo, Antonio; Perret, Pascal; Perrin-Terrin, Mathieu; Pescatore, Luca; Pesen, Erhan; Pessina, Gianluigi; Petridis, Konstantin; Petrolini, Alessandro; Picatoste Olloqui, Eduardo; Pietrzyk, Boleslaw; Pilař, Tomas; Pinci, Davide; Playfer, Stephen; Plo Casasus, Maximo; Polci, Francesco; Polok, Grzegorz; Poluektov, Anton; Polycarpo, Erica; Popov, Alexander; Popov, Dmitry; Popovici, Bogdan; Potterat, Cédric; Powell, Andrew; Prisciandaro, Jessica; Pritchard, Adrian; Prouve, Claire; Pugatch, Valery; Puig Navarro, Albert; Punzi, Giovanni; Qian, Wenbin; Rachwal, Bartolomiej; Rademacker, Jonas; Rakotomiaramanana, Barinjaka; Rangel, Murilo; Raniuk, Iurii; Rauschmayr, Nathalie; Raven, Gerhard; Redford, Sophie; Reichert, Stefanie; Reid, Matthew; dos Reis, Alberto; Ricciardi, Stefania; Richards, Alexander; Rinnert, Kurt; Rives Molina, Vincente; Roa Romero, Diego; Robbe, Patrick; Roberts, Douglas; Rodrigues, Ana Barbara; Rodrigues, Eduardo; Rodriguez Perez, Pablo; Roiser, Stefan; Romanovsky, Vladimir; Romero Vidal, Antonio; Rotondo, Marcello; Rouvinet, Julien; Ruf, Thomas; Ruffini, Fabrizio; Ruiz, Hugo; Ruiz Valls, Pablo; Sabatino, Giovanni; Saborido Silva, Juan Jose; Sagidova, Naylya; Sail, Paul; Saitta, Biagio; Salustino Guimaraes, Valdir; Sanmartin Sedes, Brais; Santacesaria, Roberta; Santamarina Rios, Cibran; Santovetti, Emanuele; Sapunov, Matvey; Sarti, Alessio; Satriano, Celestina; Satta, Alessia; Savrie, Mauro; Savrina, Darya; Schiller, Manuel; Schindler, Heinrich; Schlupp, Maximilian; Schmelling, Michael; Schmidt, Burkhard; Schneider, Olivier; Schopper, Andreas; Schune, Marie Helene; Schwemmer, Rainer; Sciascia, Barbara; Sciubba, Adalberto; Seco, Marcos; Semennikov, Alexander; Senderowska, Katarzyna; Sepp, Indrek; Serra, Nicola; Serrano, Justine; Seyfert, Paul; Shapkin, Mikhail; Shapoval, Illya; Shcheglov, Yury; Shears, Tara; Shekhtman, Lev; Shevchenko, Oksana; Shevchenko, Vladimir; Shires, Alexander; Silva Coutinho, Rafael; Sirendi, Marek; Skidmore, Nicola; Skwarnicki, Tomasz; Smith, Anthony; Smith, Edmund; Smith, Eluned; Smith, Jackson; Smith, Mark; Sokoloff, Michael; Soler, Paul; Soomro, Fatima; Souza, Daniel; Souza De Paula, Bruno; Spaan, Bernhard; Sparkes, Ailsa; Spradlin, Patrick; Stagni, Federico; Stahl, Sascha; Steinkamp, Olaf; Stevenson, Scott; Stoica, Sabin; Stone, Sheldon; Storaci, Barbara; Stracka, Simone; Straticiuc, Mihai; Straumann, Ulrich; Subbiah, Vijay Kartik; Sun, Liang; Sutcliffe, William; Swientek, Stefan; Syropoulos, Vasileios; Szczekowski, Marek; Szczypka, Paul; Szilard, Daniela; Szumlak, Tomasz; T'Jampens, Stephane; Teklishyn, Maksym; Tellarini, Giulia; Teodorescu, Eliza; Teubert, Frederic; Thomas, Christopher; Thomas, Eric; van Tilburg, Jeroen; Tisserand, Vincent; Tobin, Mark; Tolk, Siim; Tomassetti, Luca; Tonelli, Diego; Topp-Joergensen, Stig; Torr, Nicholas; Tournefier, Edwige; Tourneur, Stephane; Tran, Minh Tâm; Tresch, Marco; Tsaregorodtsev, Andrei; Tsopelas, Panagiotis; Tuning, Niels; Ubeda Garcia, Mario; Ukleja, Artur; Ustyuzhanin, Andrey; Uwer, Ulrich; Vagnoni, Vincenzo; Valenti, Giovanni; Vallier, Alexis; Vazquez Gomez, Ricardo; Vazquez Regueiro, Pablo; Vázquez Sierra, Carlos; Vecchi, Stefania; Velthuis, Jaap; Veltri, Michele; Veneziano, Giovanni; Vesterinen, Mika; Viaud, Benoit; Vieira, Daniel; Vilasis-Cardona, Xavier; Vollhardt, Achim; Volyanskyy, Dmytro; Voong, David; Vorobyev, Alexey; Vorobyev, Vitaly; Voß, Christian; Voss, Helge; de Vries, Jacco; Waldi, Roland; Wallace, Charlotte; Wallace, Ronan; Wandernoth, Sebastian; Wang, Jianchun; Ward, David; Watson, Nigel; Webber, Adam Dane; Websdale, David; Whitehead, Mark; Wicht, Jean; Wiechczynski, Jaroslaw; Wiedner, Dirk; Wiggers, Leo; Wilkinson, Guy; Williams, Matthew; Williams, Mike; Wilson, Fergus; Wimberley, Jack; Wishahi, Julian; Wislicki, Wojciech; Witek, Mariusz; Wormser, Guy; Wotton, Stephen; Wright, Simon; Wu, Suzhi; Wyllie, Kenneth; Xie, Yuehong; Xing, Zhou; Yang, Zhenwei; Yuan, Xuhao; Yushchenko, Oleg; Zangoli, Maria; Zavertyaev, Mikhail; Zhang, Feng; Zhang, Liming; Zhang, Wen Chao; Zhang, Yanxi; Zhelezov, Alexey; Zhokhov, Anatoly; Zhong, Liang; Zvyagin, Alexander


    Decays of beauty baryons to the $D^0 p h^-$ and $\\Lambda_c^+ h^-$ final states (where $h$ indicates a pion or a kaon) are studied using a data sample of $pp$ collisions, corresponding to an integrated luminosity of 1.0 fb$^{-1}$, collected by the LHCb detector. The Cabibbo-suppressed decays $\\Lambda_b^0\\to D^0 p K^-$ and $\\Lambda_b^0\\to \\Lambda_c^+ K^-$ are observed and their branching fractions are measured with respect to the decays $\\Lambda_b^0\\to D^0 p \\pi^-$ and $\\Lambda_b^0\\to \\Lambda_c^+ \\pi^-$. In addition, the first observation is reported of the decay of the neutral beauty-strange baryon $\\Xi_b^0$ to the $D^0 p K^-$ final state, and a measurement of the $\\Xi_b^0$ mass is performed. Evidence of the $\\Xi_b^0\\to \\Lambda_c^+ K^-$ decay is also reported.

  4. Drift mobility measurements in a-C:H films by time-resolved electroluminescence

    Energy Technology Data Exchange (ETDEWEB)

    Foulani, A


    Carrier transport mechanism has been studied in thin insulating hydrogenated amorphous carbon (a-C:H) films. The layers were prepared by plasma polymerization of methane (CH{sub 4}) at a frequency of 20 kHz. Electron mobility was derived from time-resolved luminescence experiments. Between the application of a rectangular voltage pulse and the first appearance of electroluminescence (EL) a time lag exists, which depends on the pulse height. Transit times are in the order of 10{sup -3} to {approx}10{sup -6} s in a voltage rabetween 10 and 25 V. And the estimated electron mobility varies accordingly from 8x10{sup -8} to {approx}10{sup -6} cm{sup 2}/(V s). The field dependence of the carriers mobility is characteristic of Poole-Frenkel-detrapping conduction model, and thus confirms the results obtained by dc experimental data.

  5. Recommended Thermal Rate Coefficients for the C + H3 + Reaction and Some Astrochemical Implications (United States)

    Vissapragada, S.; Buzard, C. F.; Miller, K. A.; O'Connor, A. P.; de Ruette, N.; Urbain, X.; Savin, D. W.


    We incorporate our experimentally derived thermal rate coefficients for C + {{{H}}}3+ forming CH+ and CH2 + into a commonly used astrochemical model. We find that the Arrhenius-Kooij equation typically used in chemical models does not accurately fit our data and instead we use a more versatile fitting formula. At a temperature of 10 K and a density of 104 cm-3, we find no significant differences in the predicted chemical abundances, but at higher temperatures of 50, 100, and 300 K we find up to factor of 2 changes. In addition, we find that the relatively small error on our thermal rate coefficients, ˜15%, significantly reduces the uncertainties on the predicted abundances compared to those obtained using the currently implemented Langevin rate coefficient with its estimated factor of 2 uncertainty.

  6. Recommended Thermal Rate Coefficients for the C + H$_3^+$ Reaction and Some Astrochemical Implications

    CERN Document Server

    Vissapragada, S; Miller, K A; O'Connor, A P; de Ruette, N; Urbain, X; Savin, D W


    We have incorporated our experimentally derived thermal rate coefficients for C + H$_3^+$ forming CH$^+$ and CH$_2^+$ into a commonly used astrochemical model. We find that the Arrhenius-Kooij equation typically used in chemical models does not accurately fit our data and use instead a more versatile fitting formula. At a temperature of 10 K and a density of 10$^4$ cm$^{-3}$, we find no significant differences in the predicted chemical abundances, but at higher temperatures of 50, 100, and 300 K we find up to factor of 2 changes. Additionally, we find that the relatively small error on our thermal rate coefficients, $\\sim15\\%$, significantly reduces the uncertainties on the predicted abundances compared to those obtained using the currently implemented Langevin rate coefficient with its estimated factor of 2 uncertainty.

  7. Total Synthesis of Verruculogen and Fumitremorgin A Enabled by Ligand-Controlled C-H Borylation. (United States)

    Feng, Yu; Holte, Dane; Zoller, Jochen; Umemiya, Shigenobu; Simke, Leah R; Baran, Phil S


    Verruculogen and fumitremorgin A are bioactive alkaloids that contain a unique eight-membered endoperoxide. Although related natural products such as fumitremorgins B and C have been previously synthesized, we report the first synthesis of the more complex, endoperoxide-containing members of this family. A concise route to verruculogen and fumitremorgin A relied not only on a hydroperoxide/indole hemiaminal cyclization, but also on the ability to access the seemingly simple starting material, 6-methoxytryptophan. An iridium-catalyzed C-H borylation/Chan-Lam procedure guided by an N-TIPS group enabled the conversion of a tryptophan derivative into a 6-methoxytryptophan derivative, proving to be a general way to functionalize the C6 position of an N,C3-disubstituted indole for the synthesis of indole-containing natural products and pharmaceuticals.

  8. Clean and Selective Catalytic C-H alkylation of Alkenes with Environmental friendly Alcohols

    KAUST Repository

    Poater, Albert


    Bearing the alkylation of alkene substrates using alcohol as solvent, catalysed by the cationic Ru-based catalyst [(C6H6)(PCy3)(CO)RuH]+, DFT calculations have been carried out to get mechanistic insights of such an environmental friendly reaction. Hard experimental conditions of Yi and coworkers [Science2011, 333, 1613] allow the formation of a C-C bond between indene and ethanol. The predicted mechanism suggests a cationic Ru-alkenyl species once two equivalents of indene interact releasing a molecule of indane subproduct. Then, oxidative addition of the Csingle bondO bond of alcohol to Ru-alkenyl species leads to Ru-alkenyl-alkyl species, followed by the reductive elimination process produces the desired alkylation product and a Ru-hydroxo complex. Finally, vinylic Csingle bondH activation and water elimination regenerates the Ru-alkenyl species. In this paper we present a full description of the complete reaction pathway along with possible alternative pathways, which are predicted to display higher upper barriers. Furthermore, the present study explains the possible reasons for the absence of undesired products such as indene dimer or hydroxylated indene in the experiments.

  9. Pricing Chinese Convertible Bonds with Dynamic Credit Risk

    Directory of Open Access Journals (Sweden)

    Ping Li


    Full Text Available To price convertible bonds more precisely, least squares Monte Carlo (LSM method is used in this paper for its advantage in handling the dependence of derivatives on the path, and dynamic credit risk is used to replace the fixed one to make the value of convertible bonds reflect the real credit risk. In the empirical study, we price convertible bonds based on static credit risk and dynamic credit risk, respectively. Empirical results indicate that the ICBC convertible bond has been overpriced, resulting from the underestimation of credit risk. In addition, when there is an issue of dividend, the conversion price will change in China's convertible bonds, while it does not change in the international convertible bonds. So we also empirically study the difference between the convertible bond's prices by assuming whether the conversion price changes or not.

  10. Photolysis and thermolysis of bis(imino)pyridine cobalt azides: C-H activation from putative cobalt nitrido complexes. (United States)

    Hojilla Atienza, Crisita Carmen; Bowman, Amanda C; Lobkovsky, Emil; Chirik, Paul J


    A series of planar aryl-substituted bis(imino)pyridine cobalt azide complexes were prepared and evaluated as synthetic precursors for the corresponding cobalt nitrido compounds. Thermolysis or photolysis of two examples resulted in intramolecular C-H activation of the benzylic positions of the aryl substituents. For the mesityl-substituted compound, C-H activation by the putative nitride resulted in formation of a neutral imine ligand and modification of the chelate by hydrogen transfer to the imine carbon.

  11. The C--H Stretching Features at 3.2--3.5 Micrometer of Polycyclic Aromatic Hydrocarbons with Aliphatic Sidegroups

    CERN Document Server

    Yang, Xuejuan; Glaser, Rainer; Zhong, Jianxin


    The so-called unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometer are ubiquitously seen in a wide variety of astrophysical regions. The UIE features are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, e.g., polycyclic aromatic hydrocarbon (PAH) molecules. The 3.3 micrometer aromatic C--H stretching feature is often accompanied by a weaker feature at 3.4 micrometer. The latter is often thought to result from the C--H stretch of aliphatic groups attached to the aromatic systems. The ratio of the observed intensity of the 3.3 micrometer aromatic C--H feature to that of the 3.4 micrometer aliphatic C--H feature allows one to estimate the aliphatic fraction of the UIE carriers, provided that the intrinsic oscillator strengths of the 3.3 micrometer aromatic C--H stretch (A3.3) and the 3.4 micrometer aliphatic C--H stretch (A3.4) are known. While previous studies on the aliphatic fraction of the UIE carriers were mostly based on the A3.4...

  12. Study of optical sensors of the form Al/a-SiC:H/c-Si(n with high sensitivity.

    Directory of Open Access Journals (Sweden)

    L. Magafas


    Full Text Available In the present work optical sensors of the form Al/a-SiC:H/c-Si(n, for different thickness of a-SiC:H thin films are stud-ied. More specifically, a-SiC:H thin films were deposited by rf sputtering technique on c-Si(n substrates for different thickness of the amorphous semiconductor and, subsequently, the samples were annealed in the temperature range from 300oC up to 675 oC. Experimental measurements of the optical response of these sensors showed that for thicknesses of a-SiC:H greater than a critical value, which depends on annealing temperature, a mechanism of losses is appeared in the region of wavelengths from 525nm up to 625nm. This behaviour is attributed to the recombination of photo-generated electrons-hole pairs in the neutral region of a-SiC:H, when this exceeds the diffusion length of minority carries, Lp. Also, the value of the reverse bias voltage appears to influence considerably the optical response of these sensors when d > Lp in the case where the a-SiC: H thin films were annealed at 600oC.

  13. Understanding Bonds - Denmark

    DEFF Research Database (Denmark)

    Rimmer, Nina Røhr


    a specified rate of interest during the life of the bond and to repay the face value of the bond (the principal) when it “matures,” or comes due. Among the types of bonds you can choose from are: Government securities, municipal bonds, corporate bonds, mortgage and asset-backed securities, federal agency...

  14. MCMini: Monte Carlo on GPGPU

    Energy Technology Data Exchange (ETDEWEB)

    Marcus, Ryan C. [Los Alamos National Laboratory


    MCMini is a proof of concept that demonstrates the possibility for Monte Carlo neutron transport using OpenCL with a focus on performance. This implementation, written in C, shows that tracing particles and calculating reactions on a 3D mesh can be done in a highly scalable fashion. These results demonstrate a potential path forward for MCNP or other Monte Carlo codes.

  15. Nanocrystal-enabled solid state bonding.

    Energy Technology Data Exchange (ETDEWEB)

    San Diego State University, San Diego, CA; Puskar, Joseph David; Tikare, Veena; Garcia Cardona, Cristina (San Diego State University, San Diego, CA); Reece, Mark; Brewer, Luke N. (Naval Postgraduate School, Monterey, CA); Holm, Elizabeth Ann


    In this project, we performed a preliminary set of sintering experiments to examine nanocrystal-enabled diffusion bonding (NEDB) in Ag-on-Ag and Cu-on-Cu using Ag nanoparticles. The experimental test matrix included the effects of material system, temperature, pressure, and particle size. The nanoparticle compacts were bonded between plates using a customized hot press, tested in shear, and examined post mortem using microscopy techniques. NEDB was found to be a feasible mechanism for low-temperature, low-pressure, solid-state bonding of like materials, creating bonded interfaces that were able to support substantial loads. The maximum supported shear strength varied substantially within sample cohorts due to variation in bonded area; however, systematic variation with fabrication conditions was also observed. Mesoscale sintering simulations were performed in order to understand whether sintering models can aid in understanding the NEDB process. A pressure-assisted sintering model was incorporated into the SPPARKS kinetic Monte Carlo sintering code. Results reproduce most of the qualitative behavior observed in experiments, indicating that simulation can augment experiments during the development of the NEDB process. Because NEDB offers a promising route to low-temperature, low-pressure, solid-state bonding, we recommend further research and development with a goal of devising new NEDB bonding processes to support Sandia's customers.

  16. Monte Carlo methods for electromagnetics

    CERN Document Server

    Sadiku, Matthew NO


    Until now, novices had to painstakingly dig through the literature to discover how to use Monte Carlo techniques for solving electromagnetic problems. Written by one of the foremost researchers in the field, Monte Carlo Methods for Electromagnetics provides a solid understanding of these methods and their applications in electromagnetic computation. Including much of his own work, the author brings together essential information from several different publications.Using a simple, clear writing style, the author begins with a historical background and review of electromagnetic theory. After addressing probability and statistics, he introduces the finite difference method as well as the fixed and floating random walk Monte Carlo methods. The text then applies the Exodus method to Laplace's and Poisson's equations and presents Monte Carlo techniques for handing Neumann problems. It also deals with whole field computation using the Markov chain, applies Monte Carlo methods to time-varying diffusion problems, and ...

  17. Use of VLC for indoors navigation with RGB LEDs and a-SiC:H photodetector (United States)

    Louro, P.; Costa, J.; Vieira, M.; Vieira, M. A.; Vygranenko, Y.


    In this research we present a Visible Light Communication (VLC) system for indoor positioning and navigation. The viability of this methodology was demonstrated in previous work for indoor positioning within the unit navigation cell. In this paper it is proposed to extend this concept for navigation in wider spaces that demand more than one navigation unit. The proposed system uses white RGB LEDs of wide divergence angle and a specific photodetector dedicated to the selective wavelengths detection of red, green and blue light. The photodetector is a multilayered pin-pin heterostructure based on a-SiC:H/a-Si:H, such that the spectral sensitivity can be controlled externally by steady state background light. The RGB emitters of the white LED were modulated with specific bit sequences and frequency to assign different optical excitations to each spatial region. The measurement of the induced photocurrent signal by the detector allows the identification of the position. For this purpose the decoding algorithm for the photocurrent signal processing uses the filtering properties of the photodetector for the recognition of the navigation cell word code, and detection of the wavelength and Fourier analysis for recognition of the signal frequency.

  18. Dioxygen activation by a non-heme iron(II) complex: formation of an iron(IV)-oxo complex via C-H activation by a putative iron(III)-superoxo species. (United States)

    Lee, Yong-Min; Hong, Seungwoo; Morimoto, Yuma; Shin, Woonsup; Fukuzumi, Shunichi; Nam, Wonwoo


    Iron(III)-superoxo intermediates are believed to play key roles in oxygenation reactions by non-heme iron enzymes. We now report that a non-heme iron(II) complex activates O(2) and generates its corresponding iron(IV)-oxo complex in the presence of substrates with weak C-H bonds (e.g., olefins and alkylaromatic compounds). We propose that a putative iron(III)-superoxo intermediate initiates the O(2)-activation chemistry by abstracting a H atom from the substrate, with subsequent generation of a high-valent iron(IV)-oxo intermediate from the resulting iron(III)-hydroperoxo species.

  19. Metropolis Methods for Quantum Monte Carlo Simulations


    Ceperley, D. M.


    Since its first description fifty years ago, the Metropolis Monte Carlo method has been used in a variety of different ways for the simulation of continuum quantum many-body systems. This paper will consider some of the generalizations of the Metropolis algorithm employed in quantum Monte Carlo: Variational Monte Carlo, dynamical methods for projector monte carlo ({\\it i.e.} diffusion Monte Carlo with rejection), multilevel sampling in path integral Monte Carlo, the sampling of permutations, ...

  20. H2 formation via the UV photo-processing of a-C:H nano-particles

    CERN Document Server

    Jones, A P


    Context. The photolysis of hydrogenated amorphous carbon, a-C(:H), dust by UV photon-irradiation in the laboratory leads to the release of H2 as well as other molecules and radicals. This same process is also likely to be important in the interstellar medium. Aims. To investigate molecule formation arising from the photo-dissociatively-driven, regenerative processing of a-C(:H) dust. Methods. We explore the mechanism of a-C(:H) grain photolysis leading to the formation of H2 and other molecules/radicals. Results. The rate constant for the photon-driven formation of H2 from a-C(:H) grains is estimated to be 2x10^-17 cm^3 s^-1. In intense radiation fields photon-driven grain decomposition will lead to fragmentation into daughter species rather than H2 formation. Conclusions. The cyclic re-structuring of arophatic a-C(:H) nano-particles appears to be a viable route to formation of H2 for low to moderate radiation field intensities (1 < G_0 < 10^2), even when the dust is warm (T ~ 50 - 100 K).

  1. Structural and medium effects on the reactions of the cumyloxyl radical with intramolecular hydrogen bonded phenols. The interplay between hydrogen-bonding and acid-base interactions on the hydrogen atom transfer reactivity and selectivity. (United States)

    Salamone, Michela; Amorati, Riccardo; Menichetti, Stefano; Viglianisi, Caterina; Bietti, Massimo


    A time-resolved kinetic study on the reactions of the cumyloxyl radical (CumO(•)) with intramolecularly hydrogen bonded 2-(1-piperidinylmethyl)phenol (1) and 4-methoxy-2-(1-piperidinylmethyl)phenol (2) and with 4-methoxy-3-(1-piperidinylmethyl)phenol (3) has been carried out. In acetonitrile, intramolecular hydrogen bonding protects the phenolic O-H of 1 and 2 from attack by CumO(•) and hydrogen atom transfer (HAT) exclusively occurs from the C-H bonds that are α to the piperidine nitrogen (α-C-H bonds). With 3 HAT from both the phenolic O-H and the α-C-H bonds is observed. In the presence of TFA or Mg(ClO4)2, protonation or Mg(2+) complexation of the piperidine nitrogen removes the intramolecular hydrogen bond in 1 and 2 and strongly deactivates the α-C-H bonds of the three substrates. Under these conditions, HAT to CumO(•) exclusively occurs from the phenolic O-H group of 1-3. These results clearly show that in these systems the interplay between intramolecular hydrogen bonding and Brønsted and Lewis acid-base interactions can drastically influence both the HAT reactivity and selectivity. The possible implications of these findings are discussed in the framework of the important role played by tyrosyl radicals in biological systems.

  2. Cross Shear Roll Bonding

    DEFF Research Database (Denmark)

    Bay, Niels; Bjerregaard, Henrik; Petersen, Søren. B;


    The present paper describes an investigation of roll bonding an AlZn alloy to mild steel. Application of cross shear roll bonding, where the two equal sized rolls run with different peripheral speed, is shown to give better bond strength than conventional roll bonding. Improvements of up to 20......-23% in bond strength are found and full bond strength is obtained at a reduction of 50% whereas 65% is required in case of conventional roll bonding. Pseudo cross shear roll bonding, where the cross shear effect is obtained by running two equal sized rolls with different speed, gives the same results....

  3. Effects of 200cH medications on mice bone marrow cells and macrophages

    Directory of Open Access Journals (Sweden)

    Dorly de F. Buchi


    Full Text Available Paracelsus once wrote: "All things are poison and nothing is without poison, only the dose permits something not to be poisonous." Latter Hahnemann formulated the law of similars, preparations which cause certain symptoms in healthy individuals if given in diluted form to patients exhibiting similar symptoms will cure it. Highly diluted natural complexes prepared according to Hahnemann’s ancient techniques may represent a new form of immunomodulatory therapy. The lack of scientific research with highly diluted products led us to investigate the in vivo and in vitro actions of commonly used medications. Here we describe the results of experimental studies aimed at verifying the effects of Mercurius solubilis, Atropa Belladonna, Lachesis muta and Bryonia alba. All medications were at 200cH dilution. Animals were maintained for 7 days and were allowed to drink the medications, which were prepared in a way that the final dilution and agitation (200cH was performed in drinking water. The medication bottle was changed and sucussed every afternoon. Co-culture of non treated mice bone marrow cells and in vitro treated peritoneal macrophages were also performed. After animal treatment the bone marrow cells were immunophenotyped with hematopoietic lineage markers on a flow cytometer. We have determined CD11b levels on bone marrow cells after culture and co-culture with treated macrophages and these macrophages were processed to scanning electron microscopy. We have observed by morphological changes that macrophages were activated after all treatments. Mercurius solubilis treated mice showed an increase in CD3 expression and in CD11b on nonadherent bone marrow cells after co-culture with in vitro treatment. Atropa Belladonna increased CD45R and decreased Ly-6G expression on bone marrow cells after animal treatment. Lachesis muta increased CD3, CD45R and, CD11c expression and decreased CD11b ex vivo and in nonadherent cells from co

  4. Solubility of C-H-O-S Volatiles in Basaltic Melts. (United States)

    Lesne, P.; Scaillet, B.


    Arc volcanism is known for his dangerousness because of the high contents H2O, CO2 and S (H2S or SO2 depending on the fO2 of the system). The behaviour of the volatiles C, H, O and S in basaltic melts is poorly known, yet the knowledge of the solubility of these volatiles is critical to understand volcanic degassing. A significant amount of work has been done to define the solubility laws of H2O, CO2 an S in silicic melts. However, such data are still scarce for basaltic liquids. To remedy this gap, we are conducting experiments on basaltic liquids at 1200°C, at pressures varying between 250 and 2000 bar and at high fO2 (NNO+2). Basaltic compositions from Vesuvius, Etna and Stromboli are equilibrated with an H2O+S and H2O+CO2+S rich fluid phase. After rapid quench, contents of H2O and CO2 in glasses are determined by using KFT and near/mid infrared spectroscopic measurements. Major elements and sulphur contents are determined by electron microprobe analyses. Microprobe analyses show that, at near H2O saturation, sulphur contents increase with pressure (from 2500 ppm at 250 bar, to 6700 ppm at 2000 bar for Etna and Stromboli compositions). The melt composition has an influence on the sulphur contents, in particular iron, as shown in previous work, and alkalies. In particular, potassium seems to have a negative role on sulphur: for similar pressure, temperature, oxygen fugacity, and bulk S content, a difference of 3% in alkalinity induces a difference of 1000 to 2000 ppm of S contents. Results for basaltic melts equilibrated with H2O+CO2+S fluid phase will be presented at the meeting. Experimental results on H2O, CO2 and S solubilities in basaltic liquids will constitute a data base for subsequent experiments on degassing processes.

  5. Ruthenium(II)-catalysed remote C-H alkylations as a versatile platform to meta-decorated arenes (United States)

    Li, Jie; Korvorapun, Korkit; de Sarkar, Suman; Rogge, Torben; Burns, David J.; Warratz, Svenja; Ackermann, Lutz


    The full control of positional selectivity is of prime importance in C-H activation technology. Chelation assistance served as the stimulus for the development of a plethora of ortho-selective arene functionalizations. In sharp contrast, meta-selective C-H functionalizations continue to be scarce, with all ruthenium-catalysed transformations currently requiring difficult to remove or modify nitrogen-containing heterocycles. Herein, we describe a unifying concept to access a wealth of meta-decorated arenes by a unique arene ligand effect in proximity-induced ruthenium(II) C-H activation catalysis. The transformative nature of our strategy is mirrored by providing a step-economical entry to a range of meta-substituted arenes, including ketones, acids, amines and phenols--key structural motifs in crop protection, material sciences, medicinal chemistry and pharmaceutical industries.

  6. Nickel-Catalyzed Oxidative C-H/N-H Isocyanide Insertion: An Efficient Synthesis of Iminoisoindolinone Derivatives. (United States)

    Hao, Wenyan; Tian, Jun; Li, Wu; Shi, Renyi; Huang, Zhiliang; Lei, Aiwen


    Transition metal-catalyzed isocyanide insertion has served as a fundamental and important chemical transformation. Classical isocyanide insertion usually occurs between organohalides and nucleophiles, which normally involves tedious and non-atom-economical prefunctionalization processes. However, oxidative C-H/N-H isocyanide insertion offers an efficient and green alternative. Herein, a nickel-catayzed oxidative C-H/N-H isocyanide insertion of aminoquinoline benzamides has been developed. Different kinds of iminoisoindolinone derivatives could be synthesized in good yields by utilizing Ni(acac)2 as the catalyst. In this transformation, isocyanide serves as an efficient C1 connector, which further inserted into two simple nucleophiles (C-H/N-H), representing an effective way to construct heterocycles.

  7. Auger electron spectroscopy, secondary ion mass spectroscopy and optical characterization of a-C-H and BN films (United States)

    Pouch, J. J.; Alterovitz, S. A.; Warner, J. D.


    The amorphous dielectrics a-C:H and BN were deposited on III-V semiconductors. Optical band gaps as high as 3 eV were measured for a-C:H generated by C4H10 plasmas; a comparison was made with bad gaps obtained from films prepared by CH4 glow discharges. The ion beam deposited BN films exhibited amorphous behavior with band gaps on the order of 5 eV. Film compositions were studied by Auger electron spectroscopy (AES), x-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS). The optical properties were characterized by ellipsometry, UV/VIS absorption, and IR reflection and transmission. Etching rates of a-C:H subjected to O2 dicharges were determined.

  8. Advancements in the Synthesis and Applications of Cationic N-Heterocycles through Transition Metal-Catalyzed C-H Activation. (United States)

    Gandeepan, Parthasarathy; Cheng, Chien-Hong


    Cationic N-heterocycles are an important class of organic compounds largely present in natural and bioactive molecules. They are widely used as fluorescent dyes for biological studies, as well as in spectroscopic and microscopic methods. These compounds are key intermediates in many natural and pharmaceutical syntheses. They are also a potential candidate for organic light-emitting diodes (OLEDs). Because of these useful applications, the development of new methods for the synthesis of cationic N-heterocycles has received a lot of attention. In particular, many C-H activation methodologies that realize high step- and atom-economies toward these compounds have been developed. In this review, recent advancements in the synthesis and applications of cationic N-heterocycles through C-H activation reactions are summarized. The new C-H activation reactions described in this review are preferred over their classical analogs.

  9. Lectures on Monte Carlo methods

    CERN Document Server

    Madras, Neal


    Monte Carlo methods form an experimental branch of mathematics that employs simulations driven by random number generators. These methods are often used when others fail, since they are much less sensitive to the "curse of dimensionality", which plagues deterministic methods in problems with a large number of variables. Monte Carlo methods are used in many fields: mathematics, statistics, physics, chemistry, finance, computer science, and biology, for instance. This book is an introduction to Monte Carlo methods for anyone who would like to use these methods to study various kinds of mathemati

  10. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G


    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  11. Palladium-catalyzed domino C-H/N-H functionalization: an efficient approach to nitrogen-bridged heteroacenes. (United States)

    Kamimoto, Natsuyo; Schollmeyer, Dieter; Mitsudo, Koichi; Suga, Seiji; Waldvogel, Siegfried R


    Palladium-catalyzed domino C-H/N-H functionalization for the synthesis of novel nitrogen-bridged thienoacenes and 10H-benzo[4,5]thieno[3,2-b]indole derivatives from dihaloarene is reported. This domino sequence consists of initial C-H functionalization of the benzo[b]thiophene moiety, followed by Buchwald-Hartwig coupling. This transformation is also useful for the synthesis of highly π-extended compounds. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Atomistic Monte Carlo simulation of lipid membranes. (United States)

    Wüstner, Daniel; Sklenar, Heinz


    Biological membranes are complex assemblies of many different molecules of which analysis demands a variety of experimental and computational approaches. In this article, we explain challenges and advantages of atomistic Monte Carlo (MC) simulation of lipid membranes. We provide an introduction into the various move sets that are implemented in current MC methods for efficient conformational sampling of lipids and other molecules. In the second part, we demonstrate for a concrete example, how an atomistic local-move set can be implemented for MC simulations of phospholipid monomers and bilayer patches. We use our recently devised chain breakage/closure (CBC) local move set in the bond-/torsion angle space with the constant-bond-length approximation (CBLA) for the phospholipid dipalmitoylphosphatidylcholine (DPPC). We demonstrate rapid conformational equilibration for a single DPPC molecule, as assessed by calculation of molecular energies and entropies. We also show transition from a crystalline-like to a fluid DPPC bilayer by the CBC local-move MC method, as indicated by the electron density profile, head group orientation, area per lipid, and whole-lipid displacements. We discuss the potential of local-move MC methods in combination with molecular dynamics simulations, for example, for studying multi-component lipid membranes containing cholesterol.

  13. Atomistic Monte Carlo Simulation of Lipid Membranes

    Directory of Open Access Journals (Sweden)

    Daniel Wüstner


    Full Text Available Biological membranes are complex assemblies of many different molecules of which analysis demands a variety of experimental and computational approaches. In this article, we explain challenges and advantages of atomistic Monte Carlo (MC simulation of lipid membranes. We provide an introduction into the various move sets that are implemented in current MC methods for efficient conformational sampling of lipids and other molecules. In the second part, we demonstrate for a concrete example, how an atomistic local-move set can be implemented for MC simulations of phospholipid monomers and bilayer patches. We use our recently devised chain breakage/closure (CBC local move set in the bond-/torsion angle space with the constant-bond-length approximation (CBLA for the phospholipid dipalmitoylphosphatidylcholine (DPPC. We demonstrate rapid conformational equilibration for a single DPPC molecule, as assessed by calculation of molecular energies and entropies. We also show transition from a crystalline-like to a fluid DPPC bilayer by the CBC local-move MC method, as indicated by the electron density profile, head group orientation, area per lipid, and whole-lipid displacements. We discuss the potential of local-move MC methods in combination with molecular dynamics simulations, for example, for studying multi-component lipid membranes containing cholesterol.

  14. First principles DFT study of weak C-H…O bonds in crystalline amino acids under pressure-alanine (United States)

    Ramaniah, Lavanya M.; Kamal, C.; Sikka, S. K.


    Many crystalline solids containing C-H…O hydrogen bonds display blue shifting of the C-H stretching frequency under pressure. No agreed explanation is available for this. Here, we use first principles density functional theory, to determine the hydrogen atom positions to understand the cause of this blue shift. No neutron diffraction is feasible due to flux limitations for this purpose. As a first case, we have taken up the study of the amino acid, alanine. We find that the C_H_…O bond in it no longer remain isolated under compression as is case at ambient pressure. The hydrogen atom in the bond has now repulsive contacts with other atoms. This results in contraction of the C-H bond length and consequently to blue shifting as is found experimentally.

  15. Monte Carlo Simulation of Aqueous Dilute Solutions of Polyhydric Alcohols (United States)

    Lilly, Arnys Clifton, Jr.

    In order to investigate the details of hydrogen bonding and solution molecular conformation of complex alcohols in water, isobaric-isothermal Monte Carlo simulations were carried out on several systems. The solutes investigated were ethanol, ethylene glycol, 1,2-propylene glycol, 1,3 -propylene glycol and glycerol. In addition, propane, which does not hydrogen bond but does form water hydrates, was simulated in aqueous solution. The complex alcohol-water systems are very nonideal in their behavior as a function of solute concentration down to very dilute solutions. The water model employed was TIP4P water^1 and the intermolecular potentials employed are of the Jorgensen type^2 in which the interactions between the molecules are represented by interaction sites usually located on nuclei. The interactions are represented by a sum of Coulomb and Lennard-Jones terms between all intermolecular pairs of sites. Intramolecular rotations in the solute are modeled by torsional potential energy functions taken from ethanol, 1-propanol and 2-propanol for C-O and C-C bond rotations. Quasi-component pair correlation functions were used to analyze the hydrogen bonding. Hydrogen bonds were classified as proton acceptor and proton donor bonds by analyzing the nearest neighbor pair correlation function between hydroxyl oxygen and hydrogen and between solvent-water hydrogen and oxygen. The results obtained for partial molar heats of solution are more negative than experimental values by 3.0 to 14 kcal/mol. In solution, all solutes reached a contracted molecular geometry with the OH groups generally on one side of the molecule. There is a tendency for the solute OH groups to hydrogen bond with water, with more proton acceptor bonds than proton donor bonds. The water -solute binding energies correlate with experimental measurements of the water-binding properties of the solute. ftn ^1Jorgensen, W. L. et al, J. Chem. Phys., 79, 926 (1983). ^2Jorgensen, W. L., J. Phys Chem., 87, 5304

  16. Optimal Overlay of Ligands with Flexible Bonds Using Differential Evolution

    DEFF Research Database (Denmark)

    Pedersen, Christian Storm; Kristensen, Thomas Greve

    When designing novel drugs, the need arise to screen databases for structures resembling active ligands, e.g. by generating a query meta-structure which summarizes these. We propose a flexible bond method for making a meta-structure and present Monte Carlo, Nelder-Mead and Differential Evolution ...

  17. Optimal Overlay of Ligands with Flexible Bonds Using Differential Evolution

    DEFF Research Database (Denmark)

    Pedersen, Christian Storm; Kristensen, Thomas Greve

    When designing novel drugs, the need arise to screen databases for structures resembling active ligands, e.g. by generating a query meta-structure which summarizes these. We propose a flexible bond method for making a meta-structure and present Monte Carlo, Nelder-Mead and Differential Evolution...

  18. Conversation with Juan Carlos Negrete. (United States)

    Negrete, Juan Carlos


    Juan Carlos Negrete is Emeritus Professor of Psychiatry, McGill University; Founding Director, Addictions Unit, Montreal General Hospital; former President, Canadian Society of Addiction Medicine; and former WHO/PAHO Consultant on Alcoholism, Drug Addiction and Mental Health.

  19. TARC: Carlo Rubbia's Energy Amplifier

    CERN Multimedia

    Laurent Guiraud


    Transmutation by Adiabatic Resonance Crossing (TARC) is Carlo Rubbia's energy amplifier. This CERN experiment demonstrated that long-lived fission fragments, such as 99-TC, can be efficiently destroyed.

  20. Monte Carlo integration on GPU


    Kanzaki, J.


    We use a graphics processing unit (GPU) for fast computations of Monte Carlo integrations. Two widely used Monte Carlo integration programs, VEGAS and BASES, are parallelized on GPU. By using $W^{+}$ plus multi-gluon production processes at LHC, we test integrated cross sections and execution time for programs in FORTRAN and C on CPU and those on GPU. Integrated results agree with each other within statistical errors. Execution time of programs on GPU run about 50 times faster than those in C...

  1. Thermochemistry and bond dissociation energies of ketones. (United States)

    Hudzik, Jason M; Bozzelli, Joseph W


    Ketones are a major class of organic chemicals and solvents, which contribute to hydrocarbon sources in the atmosphere, and are important intermediates in the oxidation and combustion of hydrocarbons and biofuels. Their stability, thermochemical properties, and chemical kinetics are important to understanding their reaction paths and their role as intermediates in combustion processes and in atmospheric chemistry. In this study, enthalpies (ΔH°(f 298)), entropies (S°(T)), heat capacities (C(p)°(T)), and internal rotor potentials are reported for 2-butanone, 3-pentanone, 2-pentanone, 3-methyl-2-butanone, and 2-methyl-3-pentanone, and their radicals corresponding to loss of hydrogen atoms. A detailed evaluation of the carbon-hydrogen bond dissociation energies (C-H BDEs) is also performed for the parent ketones for the first time. Standard enthalpies of formation and bond energies are calculated at the B3LYP/6-31G(d,p), B3LYP/6-311G(2d,2p), CBS-QB3, and G3MP2B3 levels of theory using isodesmic reactions to minimize calculation errors. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) density functional level and are used to determine the entropies and heat capacities. The recommended ideal gas-phase ΔH°(f 298), from the average of the CBS-QB3 and G3MP2B3 levels of theory, as well as the calculated values for entropy and heat capacity are shown to compare well with the available experimental data for the parent ketones. Bond energies for primary, secondary, and tertiary radicals are determined; here, we find the C-H BDEs on carbons in the α position to the ketone group decrease significantly with increasing substitution on these α carbons. Group additivity and hydrogen-bond increment values for these ketone radicals are also determined.

  2. Valence bond and von Neumann entanglement entropy in Heisenberg ladders. (United States)

    Kallin, Ann B; González, Iván; Hastings, Matthew B; Melko, Roger G


    We present a direct comparison of the recently proposed valence bond entanglement entropy and the von Neumann entanglement entropy on spin-1/2 Heisenberg systems using quantum Monte Carlo and density-matrix renormalization group simulations. For one-dimensional chains we show that the valence bond entropy can be either less or greater than the von Neumann entropy; hence, it cannot provide a bound on the latter. On ladder geometries, simulations with up to seven legs are sufficient to indicate that the von Neumann entropy in two dimensions obeys an area law, even though the valence bond entanglement entropy has a multiplicative logarithmic correction.

  3. Influence of energetic ion bombardment on W-C : H coatings deposited with W and WC targets

    NARCIS (Netherlands)

    Strondl, C; Carvalho, NM; De Hosson, JTM; Krug, TG


    Tungsten containing diamond-like carbon (W-C:H) coatings have been produced by unbalanced magnetron sputtering using two different target materials. In the first series of coatings, W has been used as target material, and in the second series, WC has been used as target material. In both series of W

  4. An overview on the applications of `Doyle catalysts’ in asymmetric cyclopropanation, cyclopropenation and C-H insertion reactions

    Indian Academy of Sciences (India)

    Thomas J Colacot


    The chiral dirhodium(II) carboxamidates are a unique class of chiral catalysts useful for asymmetric inter- and intramolecular cyclopropanation, cyclopropenation and C-H insertion reactions with excellent enantioselectivities. The broad applications of these catalysts in organic syntheses are briefly reviewed.

  5. Direct access to pyrazolo(benzo)thienoquinolines. Highly effective palladium catalysts for the intramolecular C-H heteroarylation of arenes. (United States)

    Churruca, Fátima; Hernández, Susana; Perea, María; SanMartin, Raul; Domínguez, Esther


    A short and atom-efficient strategy to obtain a series of pyrazolo(benzo)thienoquinolines is developed. Alternative catalytic systems for the key intramolecular direct heteroarylation of arenes are presented and include the first example of C-H (hetero)arylation of (hetero)arenes catalyzed by very low catalyst loadings of a palladium source.

  6. C-H activation dependent Pd-catalyzed carbonylative coupling of (hetero)aryl bromides and polyfluoroarenes. (United States)

    Lian, Zhong; Friis, Stig D; Skrydstrup, Troels


    The carbonylative coupling of aryl and heteroaryl bromides with polyfluoroarenes via palladium-catalyzed C-H activation is presented. This transformation proceeds efficiently at moderate reaction temperatures and does not require strong base or reactive intermediates. A near stoichiometric amount of CO is sufficient and the methodology can thus be easily expanded to include the preparation of [(13)C]-acyl labeled benzopolyfluorophenones.

  7. Direct sp(3)C-H acroleination of N-aryl-tetrahydroisoquinolines by merging photoredox catalysis with nucleophilic catalysis. (United States)

    Feng, Zhu-Jia; Xuan, Jun; Xia, Xu-Dong; Ding, Wei; Guo, Wei; Chen, Jia-Rong; Zou, You-Quan; Lu, Liang-Qiu; Xiao, Wen-Jing


    Sequence catalysis merging photoredox catalysis (PC) and nucleophilic catalysis (NC) has been realized for the direct sp(3) C-H acroleination of N-aryl-tetrahydroisoquinoline (THIQ). The reaction was performed under very mild conditions and afforded products in 50-91% yields. A catalytic asymmetric variant was proved to be successful with moderate enantioselectivities (up to 83 : 17 er).

  8. Tribological Performance of Hydrogenated Amorphous Carbon (a-C: H DLC Coating when Lubricated with Biodegradable Vegetal Canola Oil

    Directory of Open Access Journals (Sweden)

    H.M. Mobarak


    Full Text Available Increasing environmental awareness and demands for lowering energy consumptions are strong driving forces behind the development of the vehicles of tomorrow. Without the advances of lubricant chemistry and adequate lubricant formulation, expansion of modern engines would not have been possible. Considering environmental awareness factors as compared to mineral oils, vegetal oil based biolubricants are renewable, biodegradable, non-toxic and have a least amount of greenhouse gases. Furthermore, improvement in engine performance and transmission components, which were impossible to achieve by applying only lubricants design, is now possible through diamond like carbon (DLC coatings. DLC coatings exhibit brilliant tribological properties, such as good wear resistance and low friction. In this regard, tribological performance of a-C: H DLC coating when lubricated with Canola vegetal oil has been investigated by the help of a ball-on-flat geometry. Experimental results demonstrated that the a-C: H DLC coating exhibited better performance with Canola oil in terms of friction and wear as compared to the uncoated materials. Large amount of polar components in the Canola oil significantly improved the tribological properties of the a-C:H coating. Thus, usage of a-C: H DLC coating with Canola oil in the long run may have a positive impact on engine life.

  9. Simulation of the Efficiency of a-SiC:H/a-Si:H Tandem Multilayer Solar Cells

    CERN Document Server

    Muminov, Khikmat Kh


    In this paper we carried out theoretical study of the general issues related to the efficiency of SiC:H/a-Si:H single- and multi-junction tandem solar cells. Implementation of numerical simulations by the use of AMPS-1D program of one-dimensional analysis of microelectronic and photonic structures for the analysis of hydrogenated silicon solar cells allowed us to formulate the optimal design of new kind of multi-junction tandem solar cells, providing its most efficient operation. The numerical analysis of SiC:H/a-Si:H single-junction solar cell whith doped i-layer used as the intermediate absorbing layer (a -Si: H) placed between layers of p-type (a-SiC: H) and n-type (a-Si: H) has been conducted. It has been established that after optimizing the solar cell parameters its highest efficiency of 19.62% is achieved at 500 nm thickness of i-layer. The optimization of the newly developed multi-junction structure of a-SiC:H/a-Si:H tandem solar cell has been conducted. It has been shown numerically that its highest ...

  10. Ligand-enabled γ-C-H olefination and carbonylation: construction of β-quaternary carbon centers. (United States)

    Li, Suhua; Chen, Gang; Feng, Chen-Guo; Gong, Wei; Yu, Jin-Quan


    Monoselective γ-C-H olefination and carbonylation of aliphatic acids has been accomplished by using a combination of a quinoline-based ligand and a weakly coordinating amide directing group. The reaction provides a new route for constructing richly functionalized all-carbon quaternary carbon centers at the β-position of aliphatic acids.

  11. C-H functionalization of phenols using combined ruthenium and photoredox catalysis: in situ generation of the oxidant. (United States)

    Fabry, David C; Ronge, Meria A; Zoller, Jochen; Rueping, Magnus


    A combination of ruthenium and photoredox catalysis allowed the ortho olefination of phenols. Using visible light, the direct C-H functionalization of o-(2-pyridyl)phenols occurred, and diverse phenol ethers were obtained in good yields. The regeneration of the ruthenium catalyst was accomplished by a photoredox-catalyzed oxidative process.

  12. Rhodium-Catalyzed β-Selective Oxidative Heck-Type Coupling of Vinyl Acetate via C-H Activation. (United States)

    Zhang, Hui-Jun; Lin, Weidong; Su, Feng; Wen, Ting-Bin


    An efficient Rh(III)-catalyzed direct ortho-C-H olefination of acetanilides with vinyl acetate was developed. This protocol provides a straightforward pathway to a series of (E)-2-acetamidostyryl acetates, giving access to indole derivatives following a simple hydrolysis/cyclization process.

  13. Rhodium(III)-catalyzed C-H activation/annulation with vinyl esters as an acetylene equivalent. (United States)

    Webb, Nicola J; Marsden, Stephen P; Raw, Steven A


    The behavior of electron-rich alkenes in rhodium-catalyzed C-H activation/annulation reactions is investigated. Vinyl acetate emerges as a convenient acetylene equivalent, facilitating the synthesis of sixteen 3,4-unsubstituted isoquinolones, as well as select heteroaryl-fused pyridones. The complementary regiochemical preferences of enol ethers versus enol esters/enamides is discussed.

  14. Electrostatics determine vibrational frequency shifts in hydrogen bonded complexes. (United States)

    Dey, Arghya; Mondal, Sohidul Islam; Sen, Saumik; Ghosh, Debashree; Patwari, G Naresh


    The red-shifts in the acetylenic C-H stretching vibration of C-H∙∙∙X (X = O, N) hydrogen-bonded complexes increase with an increase in the basicity of the Lewis base. Analysis of various components of stabilization energy suggests that the observed red-shifts are correlated with the electrostatic component of the stabilization energy, while the dispersion modulates the stabilization energy.

  15. 2-Chlorovinyl tellurium dihalides, (p-tol)Te[C(H)=C(Cl)Ph]X{sub 2} for X = Cl, Br and I: variable coordination environments, supramolecular structures and docking studies in cathepsin B

    Energy Technology Data Exchange (ETDEWEB)

    Caracelli, Ignez, E-mail: ignez@ufscar.b [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Dept. de Fisica; Zukerman-Schpector, Julio; Maganhi, Stella H., E-mail: julio@power.ufscar.b [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Dept. de Quimica. Lab. de Cristalografia, Estereodinamica e Modelagem Molecular; Stefani, Helio A. [Universidade de Sao Paulo (USP), SP (Brazil). Faculdade de Ciencias Farmaceuticas. Dept. de Farmacia; Guadagnin, Rafael [Universidade Federal de Sao Paulo (Unifesp/EPM), Sao Paulo, SP (Brazil). Dept. de Quimica; Tiekink, Edward R.T., E-mail: [University of Malaya, Kuala Lumpur (Malaysia). Dept. of Chemistry


    Crystallography shows that the Te atom in each of (p-tol)Te[C(H)=C(Cl)Ph]X{sub 2}, for X = Cl (1), Br (2) and I (3), is within a distorted {Psi}-pentagonal bipyramidal geometry. An E configuration for the vinyl group in (1) precludes the formation of an intramolecular Te...Cl interaction so that an intramolecular Te{pi} interaction is found instead. The coordination environment features a linear Cl-Te-Cl arrangement with the pentagonal plane defined by the two C atoms of the organic substituents, an intermolecular TeCl contact, a Te{pi} interaction and a stereochemically active lone pair of electrons. In the X = Br (2) and I (3) structures, similar coordination geometries are found but the Te{pi} contact is replaced by an intramolecular TeCl contact owing to the adoption of a Z configuration about the vinyl bond. The differences in structure are readily explained in terms of electronic effects. Docking studies of cathepsin B with (1')-(3'), i.e. 1-3 less one Te-bound halide, show efficient binding through the agency of covalent Te-S{sub Cys29} bonds with stabilization afforded by a combination of N-H{pi}, C-H{pi} and Cl{sub vinyl} H interactions. These results comparable favorably with known inhibitors of cathepsin B suggesting the title compounds have potential biological activity. (author)

  16. Density functional theory study of O-H and C-H bond scission of methanol catalyzed by a chemisorbed oxygen layer on Cu(111) (United States)

    Li, Jonathan; Zhou, Guangwen


    Using the density-functional theory within the generalized gradient approximation, we have studied the partial oxidation of methanol on a Cu(111) surface covered with a chemisorbed oxygen layer that resembles a Cu2O layer. Adsorption energies and geometries were computed for methanol, methoxy, hydroxymethyl and formaldehyde on both clean Cu(111) and Cu2O/Cu(111) and electronic structures were computed for the reaction intermediates on Cu2O/Cu(111). We also calculated the energy barrier for partial oxidation of methanol to formaldehyde on Cu2O/Cu(111). These results show that the Cu2O monolayer slightly lowers the stability of each of the surface adsorbates and the oxygen strongly promotes hydrogen dissociation by lowering the energy barrier of methanol decomposition and causing the spontaneous dissociation of methanol into methoxy.

  17. A brief review of para-xylene oxidation to terephthalic acid as a model of primary C-H bond activation

    Institute of Scientific and Technical Information of China (English)

    Nor Aqilah Mohd Fadzil; Mohd Hasbi Ab Rahim; Gaanty Pragas Maniam


    The oxidation of para-xylene to terephthalic acid has been commercialised as the AMOCO process (Co/Mn/Br) that uses a homogeneous catalyst of cobalt and manganese together with a corrosive bromide compound as a promoter. This process is conducted in acidic medium at a high tempera-ture (175-225 °C). Concerns over environmental and safety issues have driven studies to find mild-er oxidation reactions of para-xylene. This review discussed past and current progress in the oxida-tion of para-xylene process. The discussion concentrates on the approach of green chemistry in-cluding (1) using heterogeneous catalysts with promising high selectivity and mild reaction condi-tion, (2) application of carbon dioxide as a co-oxidant, and (3) application of alternative promoters. The optimisation of para-xylene oxidation was also outlined.

  18. Negative catalytic effect of water on the reactivity of hydrogen abstraction from the C-H bond of dimethyl ether by deuterium atoms through tunneling at low temperatures (United States)

    Oba, Yasuhiro; Watanabe, Naoki; Kouchi, Akira


    We report an experimental study on the catalytic effect of solid water on the reactivity of hydrogen abstraction (H-abstraction) from dimethyl ether (DME) in the low-temperature solid DME-H2O complex. When DME reacted with deuterium atoms on a surface at 15-25 K, it was efficiently deuterated via successive tunneling H-abstraction and deuterium (D)-addition reactions. The 'effective' rate constant for DME-H2O + D was found to be about 20 times smaller than that of pure DME + D. This provides the first evidence that the presence of solid water has a negative catalytic effect on tunneling H-abstraction reactions.

  19. Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer Catalyst before Converting to a Binuclear C-H Bond Activation Product Responsible for Hydrogen Isotope Exchange. (United States)

    Iali, Wissam; Green, Gary G R; Hart, Sam J; Whitwood, Adrian C; Duckett, Simon B


    [IrCl(COE)2]2 (1) reacts with pyridine (py) and H2 to form crystallographically characterized IrCl(H)2(COE)(py)2 (2). 2 undergoes py loss to form 16-electron IrCl(H)2(COE)(py) (3), with equivalent hydride ligands. When this reaction is studied with parahydrogen, 1 efficiently achieves hyperpolarization of free py (and nicotinamide, nicotine, 5-aminopyrimidine, and 3,5-lutudine) via signal amplification by reversible exchange (SABRE) and hence reflects a simple and readily available precatayst for this process. 2 reacts further over 48 h at 298 K to form crystallographically characterized (Cl)(H)(py)(μ-Cl)(μ-H)(κ-μ-NC5H4)Ir(H)(py)2 (4). This dimer is active in the hydrogen isotope exchange process that is used in radiopharmaceutical preparations. Furthermore, while [Ir(H)2(COE)(py)3]PF6 (6) forms upon the addition of AgPF6 to 2, its stability precludes its efficient involvement in SABRE.

  20. Theoretical study of the mechanism for C-H bond activation in spin-forbidden reaction between Ti+ and C2H4

    Institute of Scientific and Technical Information of China (English)


    The mechanism of the spin-forbidden reaction Ti+(4F, 3d24s1) + C2H4 → TiC2H2+ (2A2) + H2 on both doublet and quartet potential energy surfaces has been investigated at the B3LYP level of theory. Crossing points between the potential energy surfaces and the possible spin inversion process are discussed by means of spin-orbit coupling (SOC) calculations. The strength of the SOC between the low-lying quartet state and the doublet state is 59.3 cm-1 in the intermediate complex IM1-4B2. Thus, the changes of its spin multiplicity may occur from the quartet to the doublet surface to form IM1- 2A1, leading to a sig-nificant decrease in the barrier height on the quartet PES. After the insertion intermediate IM2, two dis-tinct reaction paths on the doublet PES have been found, i.e., a stepwise path and a concerted path. The latter is found to be the lowest energy path on the doublet PES to exothermic TiC2H2+ (2A2) + H2 products, with the active barrier of 4.52 kcal/mol. In other words, this reaction proceeds in the following way: Ti++C2H4 →4IC→IM1-4B2→4,2ISC→IM1- 2A1→[2TSins]→IM2→[2TSMCTS]→IM5→TiC2H2+(2A2)+H2.

  1. Easy abstraction of a hydride anion from an alkyl C-H bond of a coordinated bis(N-heterocyclic carbene). (United States)

    Cabeza, Javier A; Damonte, Marina; García-Álvarez, Pablo; Pérez-Carreño, Enrique


    The high basicity of a trimethylene-linked bis(NHC), acting as a chelating ligand in a ruthenium(0) complex, is responsible for its involvement in a room-temperature reaction in which the metal atom to which this bis(NHC) ligand is coordinated replaces a hydride anion of the ligand trimethylene linker, which can be taken by a hydride abstractor as unusual, in that role, as [Ru3(CO)12].

  2. Active groups for oxidative activation of C-H bond in C{sub 2}-C{sub 5} paraffins on V-P-O catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii


    For the first time in scientific literature, in our joint work with Dr. G. Ladwig in 1978 it was established phase portraite of the oxide vanadium-phosphorus system within wide range of P/V ratios from 0.5 to 3.2. Some later those data were confirmed. By investigation of the properties of individual vanadium-phosphorus phases it was also shown that the active component of such catalysts in n-butane oxidation was vanadyl pyrophosphate phase (VO){sub 2}Pr{sub 2}O{sub 7}. From then the conclusion has been evidenced by numerous publications and at present it has been out of doubt practically all over the world. It was hypothized that the unique properties of (VO){sub 2}P{sub 2}O{sub 7} in the reaction of n-butane oxidation could be explained by the presence of paired vanadyl groups and nearness of the distances between neighbouring vanadyl pairs and that between the first and fourth carbon atoms in n-butane molecule. The molecule activation occured at the latter atoms by proton abstraction. A comparison of the results on n-butane and butenes oxidation over vanadyl pyrophosphate allowed to conclude that the paraffin oxidation did not take place due to the molecule dehydrogenation process at the first stage of its conversion. Up to now, more than 100 papers related to paraffins oxidation over vanadyl pyrophosphate and the physico-chemical properties of the catalyst have been published. The process of n-butane oxidation is realized in practice. But still, the question about the nature of active sites of the catalyst and the reaction mechanism remains open and provokes further investigations. The present paper deals with our opinion about the problem and the experimental results supporting it. (orig.)

  3. Indole cyanation via C-H bond activation under catalysis of Ru(Ⅲ)-exchanged NaY zeolite (RuY) as a recyclable catalyst

    Institute of Scientific and Technical Information of China (English)

    Alireza Khorshidi


    Selective 3-cyanation of indoles was achieved under heterogeneous catalysis of Ru(Ⅲ)-exchanged NaY zeolite (RuY) as a recyclable catalyst,in combination with K4[Fe(CN)6] as a nontoxic,slow cyanide releasing agent.Under the aforementioned conditions,good yields of the desired products were obtained.

  4. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts. (United States)

    de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor


    We report the synthesis, characterization, and reactivity of [LFe3 (PhPz)3 OMn((s) PhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, (57) Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe(III)2 Fe(II) Mn(II) vs. Fe(III)3 Mn(II) ) influence oxygen atom transfer in tetranuclear Fe3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.

  5. Direct oxidative arylation of aryl C - H bonds with aryl boronic acids via pd catalysis directed by the N,N-dimethylaminomethyl group. (United States)

    Zhang, Ji-Cheng; Shi, Jiang-Ling; Wang, Bi-Qin; Hu, Ping; Zhao, Ke-Qing; Shi, Zhang-Jie


    Biaryl skeletons were directly constructed via palladium-catalyzed ortho-arylation of N,N-dimethyl benzylamine with aryl boronic acids with high efficiency and high regioselectivity under open-flask conditions. The N,N-dimethylaminomethyl group was first applied as a directing group in such an oxidative coupling. Various substrates proved to be efficient coupling partners, furnishing the corresponding ortho-monoarylated or -diarylated arenes in moderate to good yields under mild conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Bipodal surface organometallic complexes with surface N-donor ligands and application to the catalytic cleavage of C-H and C-C bonds in n -Butane

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa


    We present a new generation of "true vicinal" functions well-distributed on the inner surface of SBA15: [(Sî - Si-NH 2)(≡Si-OH)] (1) and [(≡Si-NH2)2] (2). From these amine-modified SBA15s, two new well-defined surface organometallic species [(≡Si-NH-)(≡Si-O-)]Zr(CH2tBu) 2 (3) and [(≡Si-NH-)2]Zr(CH2tBu) 2 (4) have been obtained by reaction with Zr(CH2tBu) 4. The surfaces were characterized with 2D multiple-quantum 1H-1H NMR and infrared spectroscopies. Energy-filtered transmission electron microscopy (EFTEM), mass balance, and elemental analysis unambiguously proved that Zr(CH2tBu)4 reacts with these vicinal amine-modified surfaces to give mainly bipodal bis(neopentyl)zirconium complexes (3) and (4), uniformly distributed in the channels of SBA15. (3) and (4) react with hydrogen to give the homologous hydrides (5) and (6). Hydrogenolysis of n-butane catalyzed by these hydrides was carried out at low temperature (100 C) and low pressure (1 atm). While (6) exhibits a bis(silylamido)zirconium bishydride, [(≡Si-NH-)2]Zr(H) 2 (6a) (60%), and a bis(silylamido)silyloxozirconium monohydride, [(≡Si-NH-)2(≡Si-O-)]ZrH (6b) (40%), (5) displays a new surface organometallic complex characterized by an 1H NMR signal at 14.46 ppm. The latter is assigned to a (silylimido)(silyloxo)zirconium monohydride, [(≡Si-Nî)(≡Si-O-)]ZrH (5b) (30%), coexistent with a (silylamido)(silyloxo)zirconium bishydride, [(≡Si-NH-)(≡Si-O-)] Zr(H)2 (5a) (45%), and a silylamidobis(silyloxo)zirconium monohydride, [(≡Si-NH-)(≡Si-O-)2]ZrH (5c) (25%). Surprisingly, nitrogen surface ligands possess catalytic properties already encountered with silicon oxide surfaces, but interestingly, catalyst (5) with chelating [N,O] shows better activity than (6) with chelating [N,N]. © 2013 American Chemical Society.

  7. C-H and H-H bond activation via ligand dearomatization/rearomatization of a PN³P-rhodium(I) complex. (United States)

    Wang, Yuan; Zheng, Bin; Pan, Yupeng; Pan, Chengling; He, Lipeng; Huang, Kuo-Wei


    A neutral complex PN(3)P-Rh(I)Cl (2) was prepared from a reaction of the PN(3)P pincer ligand (1) with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene). Upon treatment with a suitable base, H-H and C(sp(2))-H activation reactions can be achieved through the deprotonation/reprotonation of one of the N-H arms and dearomatization/rearomatization of the central pyridine ring with the oxidation state of Rh remaining I.

  8. C-H and H-H Bond Activation via Ligand Dearomatization/Rearomatization of a PN3P-Rhodium(I) Complex

    KAUST Repository

    Huang, Kuo-Wei


    A neutral complex PN3P-Rh(I)Cl (2) was prepared from a reaction of the PN3P pincer ligand (1) with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene). Upon treatment with a suitable base, H–H and Csp2–H activation reactions can be achieved through the deprotonation/reprotonation of one of the N–H arms and dearomatization/rearomatization of the central pyridine ring with the oxidation state of Rh remaining I.

  9. Enhanced solar photons harvesting of a-SiC:H solar cells with ZBLA fluoride glasses containing rare earth ions

    Energy Technology Data Exchange (ETDEWEB)

    Song, Pei, E-mail:; Zhang, Chaomin; Zhu, Pengfei


    As encapsulation glasses for a-SiC:H cells, Yb{sup 3+}/Ce{sup 3+}-Er{sup 3+} tri-doped ZBLA fluoride glasses were prepared using the high temperature melt-quenching method and the optical characteristic of the glass were measured. Depending on the nature of rare earth doped ZBLA fluoride glasses, both near infrared (low-energy) and ultraviolet (high-energy) solar photons can be transformed into visible photons. By downshifting the ultraviolet (280–350 nm) light combined with upconverting the near infrared (900–1100 nm) light, the glass can emit strong visible (500–700 nm) light, which matches well with the spectral responsivity of a-SiC:H cells. The conversion of non-absorption photons energies by upconversion and downshifting leads to promote the improvement of a-SiC:H cells performances, and measurement shows relatively increase of 7.6%–0.8% in cell efficiencies. - Highlights: • Yb{sup 3+}-Ce{sup 3+}-Er{sup 3+} tri-doped ZBLA fluoride glasses have been prepared. • An efficient energy transfer can occur from Yb{sup 3+} and Ce{sup 3+} ions to Er{sup 3+} ions. • Both ultraviolet and near-infrared photons can be converted into visible photons. • A-SiC:H cell efficiency is effectively raised by encapsulated with RE-ZBLA glass. • The emission of glasses matched well with the spectral response of a-SiC:H cell.

  10. Three closely related 1-(naphthalen-2-yl)prop-2-en-1-ones: pseudosymmetry, disorder and supramoleular assembly mediated by C-H...π and C-Br...π interactions. (United States)

    Girisha, Marisiddaiah; Sagar, Belakavadi K; Yathirajan, Hemmige S; Rathore, Ravindranath S; Glidewell, Christopher


    It has been observed that when electron-rich naphthyl rings are present in chalcones they can participate in π-π stacking interactions, and this can play an important role in orientating inhibitors within the active sites of enzymes, while chalcones containing heterocyclic substituents additionally exhibit fungistatic and fungicidal properties. With these considerations in mind, three new chalcones containing 2-naphthyl substituents were prepared. 3-(4-Fluorophenyl)-1-(naphthalen-2-yl)prop-2-en-1-one, C19H13FO, (I), crystallizes with Z' = 2 in the space group P-1 and the four molecules in the unit cell adopt an arrangement which resembles that in the space group P21/a. Although 3-(4-bromophenyl)-1-(naphthalen-2-yl)prop-2-en-1-one, C19H13BrO, (II), with Z' = 1, is not isostructural with (I), the molecules of (I) and (II) adopt very similar conformations. In 1-(naphthalen-2-yl)-3-(thiophen-2-yl)prop-2-en-1-one, C17H12OS, (III), the thiophene unit is disordered over two sets of atomic sites, with occupancies of 0.780 (3) and 0.220 (3), which are related by a near 180° rotation of the thiophene unit about its exocyclic C-C bond. The molecules of compound (I) are linked by three independent C-H...π(arene) hydrogen bonds to form centrosymmetric octamolecular aggregates, whereas the molecules of compound (II) are linked into molecular ladders by a combination of C-H...π(arene) and C-Br...π(arene) interactions, and those of compound (III) are linked into centrosymmetric dimers by C-H...π(thiophene) interactions.

  11. Bonding and structure of copper nitrenes. (United States)

    Cundari, Thomas R; Dinescu, Adriana; Kazi, Abul B


    Copper nitrenes are of interest as intermediates in the catalytic aziridination of olefins and the amination of C-H bonds. However, despite advances in the isolation and study of late-transition-metal multiply bonded complexes, a bona fide structurally characterized example of a terminal copper nitrene has, to our knowledge, not been reported. In anticipation of such a report, terminal copper nitrenes are studied from a computational perspective. The nitrene complexes studied here are of the form (beta-diketiminate)Cu(NPh). Density functional theory (DFT), complete active space self-consistent-field (CASSCF) electronic structure techniques, and hybrid quantum mechanical/molecular mechanical (QM/MM) methods are employed to study such species. While DFT methods indicate that a triplet (S = 1) is the ground state, CASSCF calculations indicate that a singlet (S = 0) is the ground state, with only a small energy gap between the singlet and triplet. Moreover, the ground-state (open-shell) singlet copper nitrene is found to be highly multiconfigurational (i.e., biradical) and to possess a bent geometry about the nitrene nitrogen, contrasting with the linear nitrene geometry of the triplet copper nitrenes. CASSCF calculations also reveal the existence of a closed-shell singlet state with some degree of multiple bonding character for the copper-nitrene bond.

  12. High-pressure high-temperature equation of state of graphite from Monte Carlo simulations

    NARCIS (Netherlands)

    Colonna, F.; Fasolino, A.; Meijer, E.J.


    The thermoelastic behavior of graphite is experimentally accessible in a limited range of pressures and temperatures. Here we perform Monte Carlo simulations based on the accurate long range carbon bond-order potential (LCBOPII) in order to study graphite in a wider range of thermodynamic

  13. A lattice Monte Carlo study of long chain conformations at solid-polymer melt interfaces

    NARCIS (Netherlands)

    Bitsanis, Ioannis A.; Brinke, Gerrit ten


    In this paper we present a comprehensive lattice Monte Carlo study of long chain conformations at solid-polymer melt interfaces. Segmental scale interfacial features, like the bond orientational distribution were found to be independent of surface-segment energetics, and statistically identical with

  14. Multilevel sequential Monte Carlo samplers

    KAUST Repository

    Beskos, Alexandros


    In this article we consider the approximation of expectations w.r.t. probability distributions associated to the solution of partial differential equations (PDEs); this scenario appears routinely in Bayesian inverse problems. In practice, one often has to solve the associated PDE numerically, using, for instance finite element methods which depend on the step-size level . hL. In addition, the expectation cannot be computed analytically and one often resorts to Monte Carlo methods. In the context of this problem, it is known that the introduction of the multilevel Monte Carlo (MLMC) method can reduce the amount of computational effort to estimate expectations, for a given level of error. This is achieved via a telescoping identity associated to a Monte Carlo approximation of a sequence of probability distributions with discretization levels . ∞>h0>h1⋯>hL. In many practical problems of interest, one cannot achieve an i.i.d. sampling of the associated sequence and a sequential Monte Carlo (SMC) version of the MLMC method is introduced to deal with this problem. It is shown that under appropriate assumptions, the attractive property of a reduction of the amount of computational effort to estimate expectations, for a given level of error, can be maintained within the SMC context. That is, relative to exact sampling and Monte Carlo for the distribution at the finest level . hL. The approach is numerically illustrated on a Bayesian inverse problem. © 2016 Elsevier B.V.

  15. Prediction of Protein-DNA binding by Monte Carlo method (United States)

    Deng, Yuefan; Eisenberg, Moises; Korobka, Alex


    We present an analysis and prediction of protein-DNA binding specificity based on the hydrogen bonding between DNA, protein, and auxillary clusters of water molecules. Zif268, glucocorticoid receptor, λ-repressor mutant, HIN-recombinase, and tramtrack protein-DNA complexes are studied. Hydrogen bonds are approximated by the Lennard-Jones potential with a cutoff distance between the hydrogen and the acceptor atoms set to 3.2 Åand an angular component based on a dipole-dipole interaction. We use a three-stage docking algorithm: geometric hashing that matches pairs of hydrogen bonding sites; (2) least-squares minimization of pairwise distances to filter out insignificant matches; and (3) Monte Carlo stochastic search to minimize the energy of the system. More information can be obtained from our first paper on this subject [Y.Deng et all, J.Computational Chemistry (1995)]. Results show that the biologically correct base pair is selected preferentially when there are two or more strong hydrogen bonds (with LJ potential lower than -0.20) that bind it to the protein. Predicted sequences are less stable in the case of weaker bonding sites. In general the inclusion of water bridges does increase the number of base pairs for which correct specificity is predicted.

  16. Cohesion energetics of carbon allotropes: Quantum Monte Carlo study

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Hyeondeok; Kang, Sinabro; Koo, Jahyun; Lee, Hoonkyung; Kwon, Yongkyung, E-mail: [Division of Quantum Phases and Devices, School of Physics, Konkuk University, Seoul 143-701 (Korea, Republic of); Kim, Jeongnim, E-mail: [Materials Science and Technology Division and Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)


    We have performed quantum Monte Carlo calculations to study the cohesion energetics of carbon allotropes, including sp{sup 3}-bonded diamond, sp{sup 2}-bonded graphene, sp–sp{sup 2} hybridized graphynes, and sp-bonded carbyne. The computed cohesive energies of diamond and graphene are found to be in excellent agreement with the corresponding values determined experimentally for diamond and graphite, respectively, when the zero-point energies, along with the interlayer binding in the case of graphite, are included. We have also found that the cohesive energy of graphyne decreases systematically as the ratio of sp-bonded carbon atoms increases. The cohesive energy of γ-graphyne, the most energetically stable graphyne, turns out to be 6.766(6) eV/atom, which is smaller than that of graphene by 0.698(12) eV/atom. Experimental difficulty in synthesizing graphynes could be explained by their significantly smaller cohesive energies. Finally, we conclude that the cohesive energy of a newly proposed graphyne can be accurately estimated with the carbon–carbon bond energies determined from the cohesive energies of graphene and three different graphynes considered here.

  17. Cohesion Energetics of Carbon Allotropes: Quantum Monte Carlo Study

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Hyeondeok [Konkuk University, South Korea; Kang, Sinabro [Konkuk University, South Korea; Koo, Jahyun [Konkuk University, South Korea; Lee, Hoonkyung [Konkuk University, South Korea; Kim, Jeongnim [ORNL; Kwon, Yongkyung [Konkuk University, South Korea


    We have performed quantum Monte Carlo calculations to study the cohesion energetics of carbon allotropes, including sp3-bonded diamond, sp2-bonded graphene, sp-sp2 hybridized graphynes, and sp-bonded carbyne. The comput- ed cohesive energies of diamond and graphene are found to be in excellent agreement with the corresponding values de- termined experimentally for diamond and graphite, respectively, when the zero-point energies, along with the interlayer binding in the case of graphite, are included. We have also found that the cohesive energy of graphyne decreases system- atically as the ratio of sp-bonded carbon atoms increases. The cohesive energy of -graphyne, the most energetically- stable graphyne, turns out to be 6.766(6) eV/atom, which is smaller than that of graphene by 0.698(12) eV/atom. Experi- mental difficulty in synthesizing graphynes could be explained by their significantly smaller cohesive energies. Finally we conclude that the cohesive energy of a newly-proposed two-dimensional carbon network can be accurately estimated with the carbon-carbon bond energies determined from the cohesive energies of graphene and three different graphynes.

  18. Deposition and characterisation of multilayer hard coatings. Ti/TiN delta/TiC sub x N sub y /(TiC) a-C H/(Ti) a-C H

    CERN Document Server

    Burinprakhon, T


    mixture. The top layer (Ti) a-C:H was found to contain approximately 10 atomic % nitrogen, due to N sub 2 contamination during deposition caused by low conductance of N sub 2 through the nominally closed valve of the mass flow controller. The change of the CH sub 4 concentration during deposition of the top layer (Ti) a-C:H, however, showed a strong influence on the hydrogen content. The comparison of the fluorescence background of the Raman spectra revealed that hydrogen-less (Ti) a-C:H was deposited at a CH sub 4 concentration of less than 50 % flow rate in Ar. The hardness and adhesion of the multilayer coated titanium substrates were assessed by using microindentation hardness and scratch tests, respectively. A simple hardness model containing parameters that assess the contributions from the coating and the substrate to the measured hardness was developed to describe hardness variation as a function of indentation size. This model allowed the determination of a coating hardness and an effective substrate...

  19. Equilibrium Statistics: Monte Carlo Methods (United States)

    Kröger, Martin

    Monte Carlo methods use random numbers, or ‘random’ sequences, to sample from a known shape of a distribution, or to extract distribution by other means. and, in the context of this book, to (i) generate representative equilibrated samples prior being subjected to external fields, or (ii) evaluate high-dimensional integrals. Recipes for both topics, and some more general methods, are summarized in this chapter. It is important to realize, that Monte Carlo should be as artificial as possible to be efficient and elegant. Advanced Monte Carlo ‘moves’, required to optimize the speed of algorithms for a particular problem at hand, are outside the scope of this brief introduction. One particular modern example is the wavelet-accelerated MC sampling of polymer chains [406].

  20. Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH₄ Reactions on Pd Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chin, Ya-Huei; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique


    Mechanistic assessments based on kinetic and isotopic methods combined with density functional theory are used to probe the diverse pathways by which C-H bonds in CH₄ react on bare Pd clusters, Pd cluster surfaces saturated with chemisorbed oxygen (O*), and PdO clusters. C-H activation routes change from oxidative addition to Habstraction and then to σ-bond metathesis with increasing O-content, as active sites evolve from metal atom pairs (*-*) to oxygen atom (O*-O*) pairs and ultimately to Pd cationlattice oxygen pairs (Pd2+-O2-) in PdO. The charges in the CH₃ and H moieties along the reaction coordinate depend on the accessibility and chemical state of the Pd and O centers involved. Homolytic C-H dissociation prevails on bare (*-*) and O*- covered surfaces (O*-O*), while C-H bonds cleave heterolytically on Pd2+-O2- pairs at PdO surfaces. On bare surfaces, C-H bonds cleave via oxidative addition, involving Pd atom insertion into the C-H bond with electron backdonation from Pd to C-H antibonding states and the formation of tight three-center (H₃C···Pd···H)‡ transition states. On O*-saturated Pd surfaces, C-H bonds cleave homolytically on O*-O* pairs to form radical-like CH3 species and nearly formed O-H bonds at a transition state (O*···CH3 •···*OH)‡ that is looser and higher in enthalpy than on bare Pd surfaces. On PdO surfaces, site pairs consisting of exposed Pd2+ and vicinal O2-, Pdox-Oox, cleave C-H bonds heterolytically via σ-bond metathesis, with Pd2+ adding to the C-H bond, while O2- abstracts the H-atom to form a four-center (H3Cδ-···Pdox···Hδ+···Oox) transition state without detectable Pdox reduction. The latter is much more stable than transition states on *-* and O*-O* pairs and give rise to a large increase in CH₄ oxidation turnover rates at oxygen chemical

  1. Bonding with Your Baby (United States)

    ... in infant massage in your area. Breastfeeding and bottle-feeding are both natural times for bonding. Infants respond ... activities include: participating together in labor and delivery feeding ( breast or bottle ); sometimes dad forms a special bond with baby ...

  2. Monte Carlo Hamiltonian: Linear Potentials

    Institute of Scientific and Technical Information of China (English)

    LUO Xiang-Qian; LIU Jin-Jiang; HUANG Chun-Qing; JIANG Jun-Qin; Helmut KROGER


    We further study the validity of the Monte Carlo Hamiltonian method. The advantage of the method,in comparison with the standard Monte Carlo Lagrangian approach, is its capability to study the excited states. Weconsider two quantum mechanical models: a symmetric one V(x) = |x|/2; and an asymmetric one V(x) = ∞, forx < 0 and V(x) = x, for x ≥ 0. The results for the spectrum, wave functions and thermodynamical observables are inagreement with the analytical or Runge-Kutta calculations.

  3. Proton Upset Monte Carlo Simulation (United States)

    O'Neill, Patrick M.; Kouba, Coy K.; Foster, Charles C.


    The Proton Upset Monte Carlo Simulation (PROPSET) program calculates the frequency of on-orbit upsets in computer chips (for given orbits such as Low Earth Orbit, Lunar Orbit, and the like) from proton bombardment based on the results of heavy ion testing alone. The software simulates the bombardment of modern microelectronic components (computer chips) with high-energy (.200 MeV) protons. The nuclear interaction of the proton with the silicon of the chip is modeled and nuclear fragments from this interaction are tracked using Monte Carlo techniques to produce statistically accurate predictions.

  4. Theoretical Investigation of C-H Vibrational Spectroscopy. 1. Modeling of Methyl and Methylene Groups of Ethanol with Different Conformers. (United States)

    Wang, Lin; Ishiyama, Tatsuya; Morita, Akihiro


    A flexible and polarizable molecular model of ethanol is developed to extend our investigation of thermodynamic, structural, and vibrational properties of the liquid and interface. A molecular dynamics (MD) simulation with the present model confirmed that this model well reproduces a number of properties of liquid ethanol, including density, heat of vaporization, surface tension, molecular dipole moment, and trans/gauche ratio. In particular, the present model can describe vibrational IR, Raman, and sum frequency generation (SFG) spectra of ethanol and partially deuterated analogues with reliable accuracy. The improved accuracy is largely attributed to proper modeling of the conformational dependence and the intramolecular couplings including Fermi resonance in C-H vibrations. Precise dependence of torsional motions is found to be critical in representing vibrational spectra of the C-H bending. This model allows for further vibrational analysis of complicated alkyl groups widely observed in various organic molecules with MD simulation.

  5. Study of CaSO4-C-H2O System: Simulation Experiments and Thermodynamic Assessment%CaSO4-C-H2O体系研究:模拟实验与热力学探讨

    Institute of Scientific and Technical Information of China (English)

    丁康乐; 罗跃; 单敬福; 关富佳; 王莎莎


    It has been traditionally believed that the TSR solid bitumens (pyrobitumen) are the direct product of thermochemical process and has less effect over the process of thermochemical sulfate reduction (TSR) compared with hydrogen sulfide (H2S). In this study, thermochemical simulation experiment of the CaSO4-C-H2O system was conducted to investigate thermodynamic characteristics of STR in the CaSo4-C-H2O system using activated carbon (C) as a model compound of solid bitumen. The results show that CaSO4-C-H2O system initiated TSR process at the temperature of 300°C , generating products like CaCO3, H2S and CO2. The threshold temperature (300°C) is much lower than temperature range of the TSR simulation tests using hydrocarbons in both gaseous and aqueous states, and consistent with the result through thermodynamic calculations. Process simulation of TSR was conducted using the software of HSC Chemistry 5. 0. It was found that TSR in the CaSOf-C-H2O system initiated at reservoir temperatures of 25~200°C was completely controlled by kinetic factors and increasing pressure is unfavorable to initiation of TSR under a constant temperature. The intensity of TSR is likely associated with saturation concentration of CaSO4 in water: a small amount of water may contribute to better oxidizing conditions while excessive water likely restrains the process of TSR. Under the conditions of pH≤2 and certain temperature, amount of sulfate decreased with decreasing pH. However, for pH range (pH>4) formation water in sedimentary basins, effect of pH on TSR can be negligible. TSR in the system of CaSO4-C-H2O is an exothermic process, and the reaction heat increases with the increasing temperatures. It was established that reaction heat of TSR is about 12. 9-133 J/mol CaSO4 at 25~200°C. Thermodynamic studies and experimental results imply that solid bitumens (pyrobitumen) are much easily involved in TSR than gaseous or aqueous hydrocarbons.%传统认为TSR成因的固态沥青(焦

  6. Palladium-catalyzed C-H activation/intramolecular amination reaction: a new route to 3-aryl/alkylindazoles. (United States)

    Inamoto, Kiyofumi; Saito, Tadataka; Katsuno, Mika; Sakamoto, Takao; Hiroya, Kou


    A method for the catalytic C-H activation of hydrazone compounds followed by intramolecular amination is described. It requires the use of a catalytic amount of Pd(OAc)2 in the presence of Cu(OAc)2 and AgOCOCF3, which efficiently effects the cyclization to afford variously substituted indazoles. The reactions proceed under relatively mild conditions and thus tolerate a variety of functional groups, including alkoxycarbonyl and cyano groups and halogen atoms.

  7. Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C-H activation. (United States)

    Huang, Xiongyi; Groves, John T


    Since our initial report in 1976, the oxygen rebound mechanism has become the consensus mechanistic feature for an expanding variety of enzymatic C-H functionalization reactions and small molecule biomimetic catalysts. For both the biotransformations and models, an initial hydrogen atom abstraction from the substrate (R-H) by high-valent iron-oxo species (Fe(n)=O) generates a substrate radical and a reduced iron hydroxide, [Fe(n-1)-OH ·R]. This caged radical pair then evolves on a complicated energy landscape through a number of reaction pathways, such as oxygen rebound to form R-OH, rebound to a non-oxygen atom affording R-X, electron transfer of the incipient radical to yield a carbocation, R(+), desaturation to form olefins, and radical cage escape. These various flavors of the rebound process, often in competition with each other, give rise to the wide range of C-H functionalization reactions performed by iron-containing oxygenases. In this review, we first recount the history of radical rebound mechanisms, their general features, and key intermediates involved. We will discuss in detail the factors that affect the behavior of the initial caged radical pair and the lifetimes of the incipient substrate radicals. Several representative examples of enzymatic C-H transformations are selected to illustrate how the behaviors of the radical pair [Fe(n-1)-OH ·R] determine the eventual reaction outcome. Finally, we discuss the powerful potential of "radical rebound" processes as a general paradigm for developing novel C-H functionalization reactions with synthetic, biomimetic catalysts. We envision that new chemistry will continue to arise by bridging enzymatic "radical rebound" with synthetic organic chemistry.

  8. Pärt: Collage sur B-A-C-H für Kammerorschester / Hans-Christian Dadelsen

    Index Scriptorium Estoniae

    Dadelsen, Hans-Christian


    Uuest heliplaadist "Pärt: Collage sur B-A-C-H für Kammerorschester, Summa (1991) für Streichorchester, Fratres, Sinfonie Nr. 2, Festina lente, Wenn Bach Bienen gezüchtet hätte, Credo für Klavier, Chor und Orchester. Philharmonia Orchestra and Chorus, Neeme Järvi". Chandos/Koch CD 9134 (WD: 63'02")

  9. Up-scaling the production of modified a-C:H coatings in the framework of plasma polymerization processes (United States)

    Corbella, C.; Bialuch, I.; Kleinschmidt, M.; Bewilogua, K.


    Hydrogenated amorphous carbon (a-C:H) films with silicon and oxygen additions, which exhibit mechanical, tribological and wetting properties adequate for protective coating performance, have been synthesized at room temperature in a small- (0.1 m 3) and a large-scale (1 m 3) coaters by low-pressure Plasma-Activated Chemical Vapour Deposition (PACVD). Hence, a-C:H:Si and a-C:H:Si:O coatings were produced in atmospheres of tetramethylsilane (TMS) and hexamethyldisiloxane (HMDSO), respectively, excited either by radiofrequency (RF - small scale) or by pulsed-DC power (large scale). Argon was employed as a carrier gas to stabilize the glow discharge. Several series of 2-5 μm thick coatings have been prepared at different mass deposition rates, Rm, by varying total gas flow, F, and input power, W. Arrhenius-type plots of Rm/ F vs. ( W/ F) -1 show linear behaviours for both plasma reactors, as expected for plasma polymerization processes at moderated energies. The calculation of apparent activation energy, Ea, in each series permitted us to define the regimes of energy-deficient and monomer-deficient PACVD processes as a function of the key parameter W/ F. Moreover, surface properties of the modified a-C:H coatings, such as contact angle, abrasive wear rate and hardness, appear also correlated to this parameter. This work shows an efficient methodology to scale up PACVD processes from small, lab-scale plasma machines to industrial plants by the unique evaluation of macroscopic parameters of deposition.

  10. Ru(ii)-Catalyzed C-H activation and annulation of salicylaldehydes with monosubstituted and disubstituted alkynes. (United States)

    Baruah, Swagata; Kaishap, Partha Pratim; Gogoi, Sanjib


    The Ru(ii)-catalyzed C-H activation and annulation reaction of salicylaldehydes and disubstituted alkynes affords chromones in high yields. This reaction also works with terminal alkynes and tolerates a wide range of sensitive functional groups. The selectivity pattern of this Ru(ii)-catalyzed annulation reaction is different from the known Au(i), Rh(iii)-catalyzed annulation reactions of salicylaldehydes and terminal alkynes.

  11. Organic chemistry. Functionalization of C(sp3)-H bonds using a transient directing group. (United States)

    Zhang, Fang-Lin; Hong, Kai; Li, Tuan-Jie; Park, Hojoon; Yu, Jin-Quan


    Proximity-driven metalation has been extensively exploited to achieve reactivity and selectivity in carbon-hydrogen (C-H) bond activation. Despite the substantial improvement in developing more efficient and practical directing groups, their stoichiometric installation and removal limit efficiency and, often, applicability as well. Here we report the development of an amino acid reagent that reversibly reacts with aldehydes and ketones in situ via imine formation to serve as a transient directing group for activation of inert C-H bonds. Arylation of a wide range of aldehydes and ketones at the β or γ positions proceeds in the presence of a palladium catalyst and a catalytic amount of amino acid. The feasibility of achieving enantioselective C-H activation reactions using a chiral amino acid as the transient directing group is also demonstrated.

  12. Sensitivity of CLIC at 380 GeV to the top FCNC decay $t\\rightarrow cH$

    CERN Document Server

    Zarnecki, Aleksander


    In the Standard Model (SM), flavour changing neutral current (FCNC) top decays, possible at loop level only, are very strongly suppressed. Observation of any such decay would be a direct signature of physics beyond the SM. Large enhancements are possible in many "new physics" scenarios and the largest enhancement is in most cases expected for the $t\\rightarrow cH$ decay. A full study for CLIC was based on the WHIZARD simulation of FCNC top decays within the 2HDM(III) model. Beam polarization and beam-induced background were taken into account. Top pair production events with the FCNC decay $t\\rightarrow cH$ can be identified based on kinematic constrains and flavour tagging information. Due to a large overlap in the kinematic space with standard top pair events, the final signal selection-efficiency is small, at the 10% level. Expected limits on $BR(t\\rightarrow cH)\\times BR(H\\rightarrow b\\bar{b})$ are compared with earlier results based on parton level simulation.

  13. Sensitivity of CLIC at 380 GeV to the top FCNC decay $t\\rightarrow cH$

    CERN Document Server



    In the Standard Model (SM), flavour changing neutral current (FCNC) top decays, possible at loop level only, are very strongly suppressed. Observation of any such decay would be a direct signature of physics beyond the SM. Large enhancements are possible in many "new physics" scenarios and the largest enhancement is in most cases expected for the $t\\rightarrow cH$ decay. A full study for CLIC was based on the WHIZARD simulation of FCNC top decays within the 2HDM(III) model. Beam polarization and beam-induced background were taken into account. Top pair production events with the FCNC decay $t\\rightarrow cH$ can be identified based on kinematic constrains and flavour tagging information. Due to a large overlap in the kinematic space with standard top pair events, the final signal selection-efficiency is small, at the 10% level. Expected limits on $BR(t\\rightarrow cH)\\times BR(H\\rightarrow b\\bar{b})$ are compared with earlier results based on parton level simulation.

  14. Rats Born to Mothers Treated with Dexamethasone 15 cH Present Changes in Modulation of Inflammatory Process

    Directory of Open Access Journals (Sweden)

    Leoni V. Bonamin


    Full Text Available As little information about the effect of ultra high dilutions of glucocorticoid in reproduction is available in the literature, pregnant female Wistar rats (N=12 were blindly subcutaneously treated during all gestational and lactation period with: dexamethasone 4 mg/kg diluted into dexamethasone 15 cH (mixed; or dexamethasone 4 mg/kg diluted in water; or dexamethasone 15 cH, or vehicle. Parental generation had body weight, food and water consumption monitored. The F1 generation was monitored regarding to newborn development. No birth occurred in both groups treated with dexamethasone 4 mg/kg. After 60 days from birth, 12 male F1 rats were randomly selected from each remaining group and inoculated subcutaneously with 1% carrageenan into the footpad, for evaluation of inflammatory performance. Edema and histopathology of the footpad were evaluated, using specific staining methods, immunohistochemistry and digital histomorphometry. Mothers treated with mixed dexamethasone presented reduced water consumption. F1 rats born to dexamethasone 15 cH treated females presented significant increase in mast cell degranulation, decrease in monocyte percentage, increase in CD18+ PMN cells, and early expression of ED2 protein, in relation to control. The results show that the exposure of parental generation to highly diluted dexamethasone interferes in inflammation modulation in the F1 generation.

  15. Bond percolation in films (United States)

    Korneta, W.; Pytel, Z.


    Bond percolation in films with simple cubic structure is considered. It is assumed that the probability of a bond being present between nearest-neighbor sites depends on the distances to surfaces. Based on the relation between the Potts model and the bond percolation model, and using the mean-field approximation, the phase diagram and profiles of the percolation probability have been obtained.

  16. Acrylic mechanical bond tests

    Energy Technology Data Exchange (ETDEWEB)

    Wouters, J.M.; Doe, P.J.


    The tensile strength of bonded acrylic is tested as a function of bond joint thickness. 0.125 in. thick bond joints were found to posses the maximum strength while the acceptable range of joints varied from 0.063 in. to almost 0.25 in. Such joints are used in the Sudbury Neutrino Observatory.

  17. Chemical bond fundamental aspects of chemical bonding

    CERN Document Server

    Frenking, Gernot


    This is the perfect complement to ""Chemical Bonding - Across the Periodic Table"" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemica

  18. Hydrogen isotope fractionation between C-H-O species in magmatic fluids (United States)

    Foustoukos, D. I.; Mysen, B. O.


    methane in the liquid is twice that recorded in the gas phase. Accordingly, condensed-phase isotope effects are inferred to govern the evolution of H/D isotopologues, induced by differences in the solubility of the isotopic molecules driven by excess energy/entropy developed during the mixing of non-polar species in the supercritical water structure. On the contrary, at such high temperatures/-pressures statistical thermodynamic models, based on the vibrational zero point energy distributions and high-temperature anharmonicity for isotopic molecules in ideal-gas reference state, predict minimal isotope exchange. Data, therefore, demonstrate that the solvation mechanism of H-D-bearing species in magmatic fluids can impose substantial D/H fractionation effects governing the δD composition of coexisting species even at lower-crust/upper-mantle temperature conditions. 1. Foustoukos D.I. and B.O. Mysen, (2012) D/H isotopic fractionation in the H2-H2O system at supercritical water conditions: Composition and hydrogen bonding effects, Geochim. Cosmochim. Acta, 86, 88-102.

  19. Carlos Mayo and Argentine historiography

    Directory of Open Access Journals (Sweden)

    Sara E. Mata


    Full Text Available The work of Carlos Mayo is distinguished by its originality and academic excellence. Our goal has been to briefly address their valuable contributions to the Argentine historiography, particularly that relating to the agricultural history of the Río de la Plata

  20. Monte Carlo Particle Lists: MCPL

    CERN Document Server

    Kittelmann, Thomas; Knudsen, Erik B; Willendrup, Peter; Cai, Xiao Xiao; Kanaki, Kalliopi


    A binary format with lists of particle state information, for interchanging particles between various Monte Carlo simulation applications, is presented. Portable C code for file manipulation is made available to the scientific community, along with converters and plugins for several popular simulation packages.

  1. Reusable ionic liquid-catalyzed oxidative coupling of azoles and benzylic compounds via sp(3) C-N bond formation under metal-free conditions. (United States)

    Liu, Wenbo; Liu, Chenjiang; Zhang, Yonghong; Sun, Yadong; Abdukadera, Ablimit; Wang, Bin; Li, He; Ma, Xuecheng; Zhang, Zengpeng


    The heterocyclic ionic liquid-catalyzed direct oxidative amination of benzylic sp(3) C-H bonds via intermolecular sp(3) C-N bond formation for the synthesis of N-alkylated azoles under metal-free conditions is reported for the first time. The catalyst 1-butylpyridinium iodide can be recycled and reused with similar efficacies for at least eight cycles.

  2. Applications of Monte Carlo Methods in Calculus. (United States)

    Gordon, Sheldon P.; Gordon, Florence S.


    Discusses the application of probabilistic ideas, especially Monte Carlo simulation, to calculus. Describes some applications using the Monte Carlo method: Riemann sums; maximizing and minimizing a function; mean value theorems; and testing conjectures. (YP)

  3. Effect of ZnO on the interfacial bonding between Na 2O-B 2O 3-SiO 2 vitrified bond and diamond (United States)

    Wang, P. F.; Li, Zh. H.; Li, J.; Zhu, Y. M.


    Diamond composites were prepared by sintering diamond grains with low melting Na 2O-B 2O 3-SiO 2 vitrified bonds in air. The influence of ZnO on the wettability and flowing ability of Na 2O-B 2O 3-SiO 2 vitrified bonds was characterized by wetting angle, the interfacial bonding states between diamond grains and the vitrified bonds were observed by scanning electron microscope (SEM), and the micro-scale bonding mechanism in the interfaces was investigated by means of energy-dispersive spectrometer (EDS), Fourier transform infrared (FTIR) spectrometer and X-ray photoelectron spectroscopy (XPS). The experimental results showed that ZnO facilitated the dissociation of boron/silicon-oxygen polyhedra and the formation of larger amount of non-bridging oxygen in the glass network, which resulted in the increase of the vitrified bonds' wettability and the formation of -C dbnd O, -O-H and -C-H bonds on the surface of diamond grains. B and Si diffused from the vitrified bonds to the interface, and C-C, C-O, C dbnd O and C-B bond formed on the surface of sintered diamond grains during sintering process, by which the interfacial bonding between diamond grains and the vitrified bonds was strengthened.

  4. (U) Introduction to Monte Carlo Methods

    Energy Technology Data Exchange (ETDEWEB)

    Hungerford, Aimee L. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    Monte Carlo methods are very valuable for representing solutions to particle transport problems. Here we describe a “cook book” approach to handling the terms in a transport equation using Monte Carlo methods. Focus is on the mechanics of a numerical Monte Carlo code, rather than the mathematical foundations of the method.

  5. Zwitterionic and cationic bis(phosphine) platinum(II) complexes: structural, electronic, and mechanistic comparisons relevant to ligand exchange and benzene C-H activation processes. (United States)

    Thomas, J Christopher; Peters, Jonas C


    Structurally similar but charge-differentiated platinum complexes have been prepared using the bidentate phosphine ligands [Ph(2)B(CH(2)PPh(2))(2)], ([Ph(2)BP(2)], [1]), Ph(2)Si(CH(2)PPh(2))(2), (Ph(2)SiP(2), 2), and H(2)C(CH(2)PPh(2))(2), (dppp, 3). The relative electronic impact of each ligand with respect to a coordinated metal center's electron-richness has been examined using comparative molybdenum and platinum model carbonyl and alkyl complexes. Complexes supported by anionic [1] are shown to be more electron-rich than those supported by 2 and 3. A study of the temperature and THF dependence of the rate of THF self-exchange between neutral, formally zwitterionic [Ph(2)BP(2)]Pt(Me)(THF) (13) and its cationic relative [(Ph(2)SiP(2))Pt(Me)(THF)][B(C(6)F(5))(4)] (14) demonstrates that different exchange mechanisms are operative for the two systems. Whereas cationic 14 displays THF-dependent, associative THF exchange in benzene, the mechanism of THF exchange for neutral 13 appears to be a THF independent, ligand-assisted process involving an anchimeric, eta(3)-binding mode of the [Ph(2)BP(2)] ligand. The methyl solvento species 13, 14, and [(dppp)Pt(Me)(THF)][B(C(6)F(5))(4)] (15), each undergo a C-H bond activation reaction with benzene that generates their corresponding phenyl solvento complexes [Ph(2)BP(2)]Pt(Ph)(THF) (16), [(Ph(2)SiP(2))Pt(Ph)(THF)][B(C(6)F(5))(4)] (17), and [(dppp)Pt(Ph)(THF)][B(C(6)F(5))(4)] (18). Examination of the kinetics of each C-H bond activation process shows that neutral 13 reacts faster than both of the cations 14 and 15. The magnitude of the primary kinetic isotope effect measured for the neutral versus the cationic systems also differs markedly (k(C(6)H(6))/k(C(6)D(6)): 13 = 1.26; 14 = 6.52; 15 approximately 6). THF inhibits the rate of the thermolysis reaction in all three cases. Extended thermolysis of 17 and 18 results in an aryl coupling process that produces the dicationic, biphenyl-bridged platinum dimers [[(Ph(2)SiP(2))Pt](2

  6. Phosphine-directed C-H borylation reactions: facile and selective access to ambiphilic phosphine boronate esters. (United States)

    Crawford, Kristina M; Ramseyer, Timothy R; Daley, Christopher J A; Clark, Timothy B


    Ambiphilic ligands have received considerable attention over the last two decades due to their unique reactivity as organocatalysts and ligands. The iridium-catalyzed C-H borylation of phosphines is described in which the phosphine is used as a directing group to provide selective formation of arylboronate esters with unique scaffolds of ambiphilic compounds. A variety of aryl and benzylic phosphines were subjected to the reaction conditions, selectively providing stable, isolable boronate esters upon protection of the phosphine as the borane complex. After purification, the phosphine-substituted boronate esters could be deprotected and isolated in pure form.

  7. Mechanism of cooperative catalysis in a Lewis acid promoted nickel-catalyzed dual C-H activation reaction. (United States)

    Anand, Megha; Sunoj, Raghavan B


    The mechanism of cooperativity offered by AlMe(3) in a Ni-catalyzed dehydrogenative cycloaddition between substituted formamides and an alkyne is investigated by using DFT(SMD(toluene)/M06/6-31G**) methods. The preferred pathway is identified to involve dual C-H activation, with first a higher barrier formyl C(sp(2))-H oxidative insertion followed by benzylic methyl C(sp(3))-H activation. The cooperativity is traced to be of kinetic origin as evidenced by stabilized transition states when AlMe(3) is bound to the formyl group, particularly in the oxidative insertion step.

  8. C H Rautenbach, P S Dreyer en C K Oberholzer: Hulle nalatenskap en die pad vorentoe1

    Directory of Open Access Journals (Sweden)

    Johann Beukes


    Full Text Available C H Rautenbach, P S Dreyer and C K Oberholzer: Their legacy and the way ahead. This article explores the legacy of three early philosophers at the University of Pretoria (1939-1987, who contributed substantially to the Nederduitsch Hervormde Kerk's perspectives on the relation between (modern theology and (modern philosophy. The authors consider their legacy to be an essentially Kantian stabilisation of the complex and problematic relationship between reason and faith, church and society, and theology and philosophy. The article then proceeds to interpret the changes in these relationships that were brought about by the postmodern discourse.

  9. Discovery of an α-amino C-H arylation reaction using the strategy of accelerated serendipity. (United States)

    McNally, Andrew; Prier, Christopher K; MacMillan, David W C


    Serendipity has long been a welcome yet elusive phenomenon in the advancement of chemistry. We sought to exploit serendipity as a means of rapidly identifying unanticipated chemical transformations. By using a high-throughput, automated workflow and evaluating a large number of random reactions, we have discovered a photoredox-catalyzed C-H arylation reaction for the construction of benzylic amines, an important structural motif within pharmaceutical compounds that is not readily accessed via simple substrates. The mechanism directly couples tertiary amines with cyanoaromatics by using mild and operationally trivial conditions.

  10. Prediction of Bond Wire Fatigue of IGBTs in a PV Inverter Under a Long-Term Operation

    DEFF Research Database (Denmark)

    Reigosa, Paula Diaz; Wang, Huai; Yang, Yongheng


    Bond wire fatigue is one of the dominant failure mechanisms in IGBT modules under cyclic stresses. However, there are still major challenges ahead to achieve a realistic bond wire lifetime prediction in field operation. This paper proposes a Monte Carlo based analysis method to predict the lifetime...

  11. Density matrix quantum Monte Carlo

    CERN Document Server

    Blunt, N S; Spencer, J S; Foulkes, W M C


    This paper describes a quantum Monte Carlo method capable of sampling the full density matrix of a many-particle system, thus granting access to arbitrary reduced density matrices and allowing expectation values of complicated non-local operators to be evaluated easily. The direct sampling of the density matrix also raises the possibility of calculating previously inaccessible entanglement measures. The algorithm closely resembles the recently introduced full configuration interaction quantum Monte Carlo method, but works all the way from infinite to zero temperature. We explain the theory underlying the method, describe the algorithm, and introduce an importance-sampling procedure to improve the stochastic efficiency. To demonstrate the potential of our approach, the energy and staggered magnetization of the isotropic antiferromagnetic Heisenberg model on small lattices and the concurrence of one-dimensional spin rings are compared to exact or well-established results. Finally, the nature of the sign problem...

  12. Efficient kinetic Monte Carlo simulation (United States)

    Schulze, Tim P.


    This paper concerns kinetic Monte Carlo (KMC) algorithms that have a single-event execution time independent of the system size. Two methods are presented—one that combines the use of inverted-list data structures with rejection Monte Carlo and a second that combines inverted lists with the Marsaglia-Norman-Cannon algorithm. The resulting algorithms apply to models with rates that are determined by the local environment but are otherwise arbitrary, time-dependent and spatially heterogeneous. While especially useful for crystal growth simulation, the algorithms are presented from the point of view that KMC is the numerical task of simulating a single realization of a Markov process, allowing application to a broad range of areas where heterogeneous random walks are the dominate simulation cost.

  13. Adaptive Multilevel Monte Carlo Simulation

    KAUST Repository

    Hoel, H


    This work generalizes a multilevel forward Euler Monte Carlo method introduced in Michael B. Giles. (Michael Giles. Oper. Res. 56(3):607–617, 2008.) for the approximation of expected values depending on the solution to an Itô stochastic differential equation. The work (Michael Giles. Oper. Res. 56(3):607– 617, 2008.) proposed and analyzed a forward Euler multilevelMonte Carlo method based on a hierarchy of uniform time discretizations and control variates to reduce the computational effort required by a standard, single level, Forward Euler Monte Carlo method. This work introduces an adaptive hierarchy of non uniform time discretizations, generated by an adaptive algorithmintroduced in (AnnaDzougoutov et al. Raùl Tempone. Adaptive Monte Carlo algorithms for stopped diffusion. In Multiscale methods in science and engineering, volume 44 of Lect. Notes Comput. Sci. Eng., pages 59–88. Springer, Berlin, 2005; Kyoung-Sook Moon et al. Stoch. Anal. Appl. 23(3):511–558, 2005; Kyoung-Sook Moon et al. An adaptive algorithm for ordinary, stochastic and partial differential equations. In Recent advances in adaptive computation, volume 383 of Contemp. Math., pages 325–343. Amer. Math. Soc., Providence, RI, 2005.). This form of the adaptive algorithm generates stochastic, path dependent, time steps and is based on a posteriori error expansions first developed in (Anders Szepessy et al. Comm. Pure Appl. Math. 54(10):1169– 1214, 2001). Our numerical results for a stopped diffusion problem, exhibit savings in the computational cost to achieve an accuracy of ϑ(TOL),from(TOL−3), from using a single level version of the adaptive algorithm to ϑ(((TOL−1)log(TOL))2).

  14. Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination. (United States)

    Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong


    Delavatine A (1) is a structurally unusual isoquinoline alkaloid isolated from Incarvillea delavayi. The first and gram-scale total synthesis of 1 was accomplished in 13 steps (the longest linear sequence) from commercially available starting materials. We exploited an isoquinoline construction strategy and developed two reactions, namely Rh-catalyzed asymmetric hydrogenation of indene-type tetrasubstituted olefins and kinetic resolution of β-alkyl phenylethylamine derivatives through Pd-catalyzed triflamide-directed C-H olefination. The substrate scope of the first reaction covered unfunctionalized olefins and those containing polar functionalities such as sulfonamides. The kinetic resolution provided a collection of enantioenriched indane and tetralin-based triflamides, including those bearing quaternary chiral centers. The selectivity factor (s) exceeded 100 for a number of substrates. These reactions enabled two different yet related approaches to a key intermediate 28 in excellent enantiopurity. In the synthesis, the triflamide served as not only an effective directing group for C-H bond activation but also a versatile functional group for further elaborations. The relative and absolute configurations of delavatine A were unambiguously assigned by the syntheses of the natural product and its three stereoisomers. Their cytotoxicity against a series of cancer cell lines were evaluated.

  15. Monte Carlo simulations of the HP model (the "Ising model" of protein folding) (United States)

    Li, Ying Wai; Wüst, Thomas; Landau, David P.


    Using Wang-Landau sampling with suitable Monte Carlo trial moves (pull moves and bond-rebridging moves combined) we have determined the density of states and thermodynamic properties for a short sequence of the HP protein model. For free chains these proteins are known to first undergo a collapse "transition" to a globule state followed by a second "transition" into a native state. When placed in the proximity of an attractive surface, there is a competition between surface adsorption and folding that leads to an intriguing sequence of "transitions". These transitions depend upon the relative interaction strengths and are largely inaccessible to "standard" Monte Carlo methods.

  16. Equilibrium CO bond lengths (United States)

    Demaison, Jean; Császár, Attila G.


    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  17. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G


    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  18. Mapping lipid and collagen by multispectral photoacoustic imaging of chemical bond vibration (United States)

    Wang, Pu; Wang, Ping; Wang, Han-Wei; Cheng, Ji-Xin


    Photoacoustic microscopy using vibrational overtone absorption as a contrast mechanism allows bond-selective imaging of deep tissues. Due to the spectral similarity of molecules in the region of overtone vibration, it is difficult to interrogate chemical components using photoacoustic signal at single excitation wavelength. Here we demonstrate that lipids and collagen, two critical markers for many kinds of diseases, can be distinguished by multispectral photoacoustic imaging of the first overtone of C-H bond. A phantom consisting of rat-tail tendon and fat was constructed to demonstrate this technique. Wavelengths between 1650 and 1850 nm were scanned to excite both the first overtone and combination bands of C-H bonds. B-scan multispectral photoacoustic images, in which each pixel contains a spectrum, were analyzed by a multivariate curve resolution-alternating least squares algorithm to recover the spatial distribution of collagen and lipids in the phantom.

  19. Computational Exploration of Rh(III)/Rh(V) and Rh(III)/Rh(I) Catalysis in Rhodium(III)-Catalyzed C-H Activation Reactions of N-Phenoxyacetamides with Alkynes. (United States)

    Yang, Yun-Fang; Houk, K N; Wu, Yun-Dong


    The selective rhodium-catalyzed functionalization of arenes is greatly facilitated by oxidizing directing groups that act both as directing groups and internal oxidants. We report density functional theory (B3LYP and M06) investigations on the mechanism of rhodium(III)-catalyzed redox coupling reaction of N-phenoxyacetamides with alkynes. The results elucidated the role of the internal oxidizing directing group, and the role of Rh(III)/Rh(I) and Rh(III)/Rh(V) catalysis of C-H functionalizations. A novel Rh(III)-Rh(V)-Rh(III) cycle successfully rationalizes recent experimental observations by Liu and Lu et al. ( Liu , G. Angew. Chem. Int. Ed. 2013 , 52 , 6033 ) on the reactions of N-phenoxyacetamides with alkynes in different solvents. Natural Bond Orbital (NBO) analysis confirms the identity of Rh(V) intermediate in the catalytic cycle.

  20. Two-dimensional supramolecular networks via C-H$\\cdots$Cl and N-H$\\cdots$Cl interactions utilizing bidentate neutral pyridine amide coordinated MnIICl2 tectons

    Indian Academy of Sciences (India)

    Wilson Jacob; Rabindranath Mukherjee


    Reaction of -(phenyl)-2-pyridinecarboxamide (HL1) and -(-tolyl)-2-pyridinecarboxamide (HL2) ligands with MnCl2.4H2O affords complexes [(HL1)2MnCl2] 1 and [(HL2)2MnCl2] 2. The structures of 1 and 2 were determined by three-dimensional X-ray crystallography revealing that the MnII ions assume distorted octahedral geometry with coordination by two HL1/HL2 ligands providing two pyridine N and two amide O and two chloride ions. Notably, secondary interactions [C-H$\\cdots$Cl (pyridine 3-H hydrogen) and N-H$\\cdots$Cl (amide NH hydrogen)] triggered by MnII-coordinated chloride ions acting as hydrogen bonding acceptors generate self-complementary dimeric tectons, which lead to 2D supramolecular architectures.

  1. Quantum Monte Carlo: Faster, More Reliable, And More Accurate (United States)

    Anderson, Amos Gerald


    The Schrodinger Equation has been available for about 83 years, but today, we still strain to apply it accurately to molecules of interest. The difficulty is not theoretical in nature, but practical, since we're held back by lack of sufficient computing power. Consequently, effort is applied to find acceptable approximations to facilitate real time solutions. In the meantime, computer technology has begun rapidly advancing and changing the way we think about efficient algorithms. For those who can reorganize their formulas to take advantage of these changes and thereby lift some approximations, incredible new opportunities await. Over the last decade, we've seen the emergence of a new kind of computer processor, the graphics card. Designed to accelerate computer games by optimizing quantity instead of quality in processor, they have become of sufficient quality to be useful to some scientists. In this thesis, we explore the first known use of a graphics card to computational chemistry by rewriting our Quantum Monte Carlo software into the requisite "data parallel" formalism. We find that notwithstanding precision considerations, we are able to speed up our software by about a factor of 6. The success of a Quantum Monte Carlo calculation depends on more than just processing power. It also requires the scientist to carefully design the trial wavefunction used to guide simulated electrons. We have studied the use of Generalized Valence Bond wavefunctions to simply, and yet effectively, captured the essential static correlation in atoms and molecules. Furthermore, we have developed significantly improved two particle correlation functions, designed with both flexibility and simplicity considerations, representing an effective and reliable way to add the necessary dynamic correlation. Lastly, we present our method for stabilizing the statistical nature of the calculation, by manipulating configuration weights, thus facilitating efficient and robust calculations. Our

  2. CARLOS FUENTES Y SU INCURSIÓN EN LA NARRATIVA POLICIAL Carlos Fuentes and his attempts at detective stories

    Directory of Open Access Journals (Sweden)

    Jaime Alberto Galgani


    Full Text Available La única obra de Carlos Fuentes perteneciente al género policial es La cabeza de la hidra (1978. Centrada en las problemáticas asociadas con el contrabando de petróleo hacia los Estados Unidos, durante la década de los 70, este relato se ubica en el contexto de la novela negra latinoamericana, presentando ciertos rasgos que la acercan al neopolicial. Con una notable hibridación de géneros, se presenta la parodia narrativa de un detective que viene a ser la versión invertida, latinoamericana, de James Bond. El artículo indaga en la novela para determinar la función que el género policial cumple en ella.The only work by Carlos Fuentes belonging to the detective story genre is La cabeza de la hidra (1978. This story, which centers on problems relating to oil smuggling into the United States during the 70s, is to be found within the contexts of the Latin-American black novel, presenting certain features which approximate the neo-detective narrative. With a remarkable hybridization of genres, the narrative parody of a detective is presented which happens to be the Latin-American opposite versión of James Bond. The article analyses the novel with the purpose of determining the function that the neo-detective genre performs in it.

  3. The design, construction and testing of a microcombustion calorimeter suitable for organic compounds containing C, H and O

    Energy Technology Data Exchange (ETDEWEB)

    Davalos, Juan Z.; Roux, M. Victoria [CSIC, Lab. de Termoquimica, Madrid (Spain)


    To obtain reliable standard energies of combustion with small amounts of C, H, O compounds, a new microcombustion calorimetry system has been set up. The design, construction, calibration and measurement experiments are described. The system includes a commercial combustion bomb with an internal volume of 22 cm{sup 3}. Samples of around 80 mg are suitable if one wants to retain the same levels of accuracy and reproducibility as those in macrocombustion experiments. Calibration of the calorimeter was performed using benzoic acid. {delta} (Calorimeter) = 2083.74{+-}0.48JK{sup -1} was obtained. Combustion measurements using m-methoxybenzoic acid were made in order to verify the chemistry of the combustion process involved in the corresponding analysis of results and the accuracy of the measurement of combustion energy. The uncertainty of the results shows that the instrument described and the experimental procedure used for the determination of enthalpies of formation of compounds containing C, H and O provide a high reliability. (Author)

  4. Kinetic solvent effects on the reactions of the cumyloxyl radical with tertiary amides. Control over the hydrogen atom transfer reactivity and selectivity through solvent polarity and hydrogen bonding. (United States)

    Salamone, Michela; Mangiacapra, Livia; Bietti, Massimo


    A laser flash photolysis study on the role of solvent effects on hydrogen atom transfer (HAT) from the C-H bonds of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-formylpyrrolidine (FPRD), and N-acetylpyrrolidine (APRD) to the cumyloxyl radical (CumO(•)) was carried out. From large to very large increases in the HAT rate constant (kH) were measured on going from MeOH and TFE to isooctane (kH(isooctane)/kH(MeOH) = 5-12; kH(isooctane)/kH(TFE) > 80). This behavior was explained in terms of the increase in the extent of charge separation in the amides determined by polar solvents through solvent-amide dipole-dipole interactions and hydrogen bonding, where the latter interactions appear to play a major role with strong HBD solvents such as TFE. These interactions increase the electron deficiency of the amide C-H bonds, deactivating these bonds toward HAT to an electrophilic radical such as CumO(•), indicating that changes in solvent polarity and hydrogen bonding can provide a convenient method for deactivation of the C-H bond of amides toward HAT. With DMF, a solvent-induced change in HAT selectivity was observed, suggesting that solvent effects can be successfully employed to control the reaction selectivity in HAT-based procedures for the functionalization of C-H bonds.

  5. Geometry and bond-length alternation in nonlinear optical materials. I. Standard parameters in two precursors. (United States)

    Gainsford, Graeme J; Bhuiyan, M Delower H; Kay, Andrew J


    2-{3-Cyano-4-[4-(N-formylanilino)-trans-1,3-butadienyl]-5,5-dimethyl-2,5-dihydrofuran-2-ylidene}propanedinitrile, C(22)H(18)N(4)O(2), (I), and 2-{3-cyano-4-[6-(N-formylanilino)-trans,trans-1,3,5-hexatrienyl]-5,5-dimethyl-2,5-dihydrofuran-2-ylidene}propanedinitrile, C(24)H(20)N(4)O(2), (II), show the alternating single/double-bond behaviour of push-pull chromophores. In the two structures, the planar polyene chains are twisted with respect to the furanylidene ring by 18.2 (2) and 12.4 (2) degrees , respectively. Comparison with structures of related and parent molecules shows subtle but consistent bond-length variations consistent with charge-delocalized structures. Crystal cohesion is provided by various sets of hydrogen bonds, viz. C-H(methyl)...N(cyano) and bifurcated (C=C-H)(2)...O=C in (I), and C-H(methyl/phenyl)...O and C=C-H...N(cyano) in (II).

  6. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter


    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation energie

  7. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter


    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation

  8. The problem of dose in homeopathy: evaluation of the effect of high dilutions of Arsenicum album 30cH on rats intoxicated with arsenic.

    Directory of Open Access Journals (Sweden)

    Gabriela Cristina Gomes Rodrigues


    Full Text Available Background: Although scientific studies have confirmed the action of homeopathic high dilutions in living organisms an endless debate on the choice of the most fitting dilution, the frequency of administration and the dose (amount of medicine still remains. Aims: This study sought to assess the in vivo effect of 2 different concentrations of Arsenicum album 30cH in order to elucidate some problems in the homeopathic notion of dose. Methods: Male Wistar rats previously intoxicated with sodium arsenate by peritoneal injection were treated with undiluted Ars 30cH and Ars 30cH in 1% solution administered by oral route. Atomic absorption spectroscopy was employed to measure the levels of arsenic retained in the animals as well as the amounts eliminated through urine. Urine samples were collected before and after and during treatment. A positive control group (intoxicated animals and negative control group (non-intoxicated animals were administered only the vehicle used to prepare the medicine (ethanol. Results: The groups treated with undiluted Ars 30cH and Ars 30cH in 1% solution eliminated significant amounts of arsenic through urine when compared to the control groups. The group treated with undiluted Ars 30cH eliminated significantly higher amounts of arsenic than the group treated with the same medicine in 1% solution. Conclusion: These results suggest that undiluted Ars 30cH was more effective than in 1% solution in this experimental model.

  9. The dissociative bond. (United States)

    Gordon, Nirit


    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  10. The samurai bond market



    Issuance in the samurai bond market has more than tripled over the past several years. Some observers have attributed this growth to a systematic underestimation of credit risk in the market. A detailed review of credit quality, ratings differences, and initial issue pricing in the samurai bond market, however, turns up little evidence to support this concern.

  11. Weak C-H$\\cdots$F-C interactions in carboxylate anion binding: Synthesis, spectroscopic and X-ray structural studies of [Co(phen)2CO3]2 (C7H3O2FCl)Cl$\\cdots$11H2O and [Co(phen)2CO3](C7H3NO4Cl)$\\cdot$6H2O

    Indian Academy of Sciences (India)

    A Singh; R P Sharma; T Aree; P Venugopalan


    Two new complex salts containing 2,5-substituted benzoate ions, [Co(phen)2CO3]2 (C7H3O2FCl)Cl$\\cdot$11H2O (1) and [Co(phen)2CO3](C7H3NO4Cl)$\\cdot$6H2O (2) (where phen = 1,10-phenanthroline, C7H3O2FCl = 2-chloro-5-fluorobenzoate (cfbz) and C7H3NO4Cl = 2-chloro-5-nitrobenzoate(cnbz)) were synthesized by reacting carbonatobis(1,10-phenanthroline)cobalt(III) chloride with appropriate salts in aqueous medium. A detailed packing analysis has been undertaken to delineate the role of second sphere C-H$\\cdots$F and C-H$\\cdots$O interactions amid other heteroatom interactions. The complex salts have been characterized by elemental analyses, spectroscopic studies (IR, UV/Visible, multinuclear NMR), conductance and solubility product measurements. Single crystal X-ray structure determination revealed ionic structures of both the complex salts having discrete ions along with lattice water molecules. Crystal lattice is stabilized by a variety of hydrogen bonding interactions, i.e. O-H$\\cdots$O, C-H$\\cdots$O and C-H$\\cdots$F involving second sphere coordination besides - interaction. Furthermore, packing analyses reveal that C-H…F interactions can manifest even in the presence of a large number of heteroatom interactions.

  12. Opto-electronic properties of P-doped nc-Si-QD/a-SiC:H thin films as foundation layer for all-Si solar cells in superstrate configuration (United States)

    Kar, Debjit; Das, Debajyoti


    With the advent of nc-Si solar cells having improved stability, the efficient growth of nc-Si i-layer of the top cell of an efficient all-Si solar cell in the superstrate configuration prefers nc-Si n-layer as its substrate. Accordingly, a wide band gap and high conducting nc-Si alloy material is a basic requirement at the n-layer. Present investigation deals with the development of phosphorous doped n-type nanocrystalline silicon quantum dots embedded in hydrogenated amorphous silicon carbide (nc-Si-QD/a-SiC:H) hetero-structure films, wherein the optical band gap can be widened by the presence of Si-C bonds in the amorphous matrix and the embedded high density tiny nc-Si-QDs could provide high electrical conductivity, particularly in P-doped condition. The nc-Si-QDs simultaneously facilitate further widening of the optical band gap by virtue of the associated quantum confinement effect. A complete investigation has been made on the electrical transport phenomena involving charge transfer by tunneling and thermionic emission prevailing in n-type nc-Si-QD/a-SiC:H thin films. Their correlation with different phases of the specific heterostructure has been carried out for detailed understanding of the material, in order to improve its device applicability. The n-type nc-Si-QD/a-SiC:H films exhibit a thermally activated electrical transport above room temperature and multi-phonon hopping (MPH) below room temperature, involving defects in the amorphous phase and the grain-boundary region. The n-type nc-Si-QD/a-SiC:H films grown at ˜300 °C, demonstrating wide optical gap ˜1.86-1.96 eV and corresponding high electrical conductivity ˜4.5 × 10-1-1.4 × 10-2 S cm-1, deserve to be an effective foundation layer for the top nc-Si sub-cell of all-Si solar cells in n-i-p structure with superstrate configuration.

  13. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael


    Corporate financing is the choice between capital generated by the corporation and capital from external investors. However, since the financial crisis shook the markets in 2007–2008, financing opportunities through the classical means of financing have decreased. As a result, corporations have...... to think in alternative ways such as issuing corporate bonds. A market for corporate bonds exists in countries such as Norway, Germany, France, the United Kingdom and the United States, while Denmark is still behind in this trend. Some large Danish corporations have instead used foreign corporate bonds...... markets. However, NASDAQ OMX has introduced the First North Bond Market in December 2012 and new regulatory framework came into place in 2014, which may contribute to a Danish based corporate bond market. The purpose of this article is to present the regulatory changes in Denmark in relation to corporate...

  14. Carlos Battilana: Profesor, Gestor, Amigo

    Directory of Open Access Journals (Sweden)

    José Pacheco


    Full Text Available El Comité Editorial de Anales ha perdido a uno de sus miembros más connotados. Brillante docente de nuestra Facultad, Carlos Alberto Battilana Guanilo (1945-2009 supo transmitir los conocimientos y atraer la atención de sus auditorios, de jóvenes estudiantes o de contemporáneos ya no tan jóvenes. Interesó a sus alumnos en la senda de la capacitación permanente y en la investigación. Por otro lado, comprometió a médicos distinguidos a conformar y liderar grupos con interés en la ciencia-amistad. Su vocación docente lo vinculó a facultades de medicina y academias y sociedades científicas, en donde coordinó cursos y congresos de grato recuerdo. Su producción científica la dedicó a la nefrología, inmunología, cáncer, costos en el tratamiento médico. Su capacidad gestora y de liderazgo presente desde su época de estudiante, le permitió llegar a ser director regional de un laboratorio farmacéutico de mucho prestigio, organizar una facultad de medicina y luego tener el cargo de decano de la facultad de ciencias de la salud de dicha universidad privada. Carlos fue elemento importante para que Anales alcanzara un sitial de privilegio entre las revistas biomédicas peruanas. En la semblanza que publicamos tratamos de resumir apretadamente la trayectoria de Carlos Battilana, semanas después de su partida sin retorno.

  15. Cuartel San Carlos. Yacimiento veterano

    Directory of Open Access Journals (Sweden)

    Mariana Flores


    Full Text Available El Cuartel San Carlos es un monumento histórico nacional (1986 de finales del siglo XVIII (1785-1790, caracterizado por sufrir diversas adversidades en su construcción y soportar los terremotos de 1812 y 1900. En el año 2006, el organismo encargado de su custodia, el Instituto de Patrimonio Cultural del Ministerio de Cultura, ejecutó tres etapas de exploración arqueológica, que abarcaron las áreas Traspatio, Patio Central y las Naves Este y Oeste de la edificación. Este trabajo reseña el análisis de la documentación arqueológica obtenida en el sitio, a partir de la realización de dicho proyecto, denominado EACUSAC (Estudio Arqueológico del Cuartel San Carlos, que representa además, la tercera campaña realizada en el sitio. La importancia de este yacimiento histórico, radica en su participación en los acontecimientos que propiciaron conflictos de poder durante el surgimiento de la República y en los sucesos políticos del siglo XX. De igual manera, se encontró en el sitio una amplia muestra de materiales arqueológicos que reseñan un estilo de vida cotidiana militar, así como las dinámicas sociales internas ocurridas en el San Carlos, como lugar estratégico para la defensa de los diferentes regímenes que atravesó el país, desde la época del imperialismo español hasta nuestros días.

  16. Monte Carlo approach to turbulence

    Energy Technology Data Exchange (ETDEWEB)

    Dueben, P.; Homeier, D.; Muenster, G. [Muenster Univ. (Germany). Inst. fuer Theoretische Physik; Jansen, K. [DESY, Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Mesterhazy, D. [Humboldt Univ., Berlin (Germany). Inst. fuer Physik


    The behavior of the one-dimensional random-force-driven Burgers equation is investigated in the path integral formalism on a discrete space-time lattice. We show that by means of Monte Carlo methods one may evaluate observables, such as structure functions, as ensemble averages over different field realizations. The regularization of shock solutions to the zero-viscosity limit (Hopf-equation) eventually leads to constraints on lattice parameters required for the stability of the simulations. Insight into the formation of localized structures (shocks) and their dynamics is obtained. (orig.)

  17. Luis Carlos López

    Directory of Open Access Journals (Sweden)

    Rafael Maya


    Full Text Available Entre los poetasa del Centenario tuvo Luis Carlos López mucha popularidad en el extranjero, desde la publicación de su primer libro. Creo que su obra llamó la atención de filósofos como Unamuno y, si no estoy equivocado, Darío se refirió a ella en términos elogiosos. En Colombia ha sido encomiada hiperbólicamente por algunos, a tiemp que otros no le conceden mayor mérito.

  18. Carlos Restrepo. Un verdadero Maestro


    Pelayo Correa


    Carlos Restrepo fue el primer profesor de Patología y un miembro ilustre del grupo de pioneros que fundaron la Facultad de Medicina de la Universidad del Valle. Estos pioneros convergieron en Cali en la década de 1950, en posesión de un espíritu renovador y creativo que emprendió con mucho éxito la labor de cambiar la cultura académica del Valle del Cauca. Ellos encontraron una sociedad apacible, que disfrutaba de la generosidad de su entorno, sin deseos de romper las tradiciones centenarias...

  19. Synthesis of trifluoromethylated isoxazoles and their elaboration through inter- and intra-molecular C-H arylation. (United States)

    Poh, Jian-Siang; García-Ruiz, Cristina; Zúñiga, Andrea; Meroni, Francesca; Blakemore, David C; Browne, Duncan L; Ley, Steven V


    We report conditions for the preparation of a range of trifluoromethylated isoxazole building blocks through the cycloaddition reaction of trifluoromethyl nitrile oxide. It was found that controlling the rate (and therefore concentration) of the formation of the trifluoromethyl nitrile oxide was Critical for the preferential formation of the desired isoxazole products versus the furoxan dimer. Different conditions were optimised for both aryl- and alkyl-substituted alkynes. In addition, the reactivity at the isoxazole 4-position has been briefly explored for these building blocks. Conditions for intermolecular C-H arylation, lithiation and electrophile quench, and alkoxylation were all identified with brief substrate scoping that signifies useful tolerance to a range of functionalities. Finally, complementary processes for structural diversification through either intramolecular cyclisation or intermolecular cross-coupling were developed.

  20. Ru(II)-Catalyzed β-Carboline Directed C-H Arylation and Isolation of Its Cycloruthenated Intermediates. (United States)

    Rajkumar, Subramani; Karthik, Shanmugam; Gandhi, Thirumanavelan


    A Ru(II)-catalyzed C-H arylation approach has been developed utilizing β-carboline alkaloids as the directing group. Selective formations of diarylated products from moderate to excellent yields were accomplished. Broad substrate scope with excellent functional group tolerance for C1-phenyl/thienyl/PAHs-β-carbolines was demonstrated. X-ray crystal structure of cycloruthenated complex 2cr and no arylation reaction with model substrate 13 strongly suggests that N2 is the directing group than N9 in C1-aryl-β-carbolines. Catalytic properties and stability of the cycloruthenated complexes have been explored. Library of biologically relevant new β-carboline derivatives and isolation of its cycloruthenated intermediates are the highlights of this work.

  1. A concise synthesis of (±)-pregabalin via intramolecular C-H insertion of N-cumyl á-diazoacetamide

    Institute of Scientific and Technical Information of China (English)

    CHEN Zhen-liang; LIU Wei-jun; CHEN Zhi-yong; Jiang Yao-zhong; HU Wen-hao


    Pregabalin 1 (3-aminomethyl-5-methyl hexanoic acid) is a potent anticonvulsant related to the inhibitory neurotransmitter a-aminobutyric acid (GABA).1 In preclinical trials of anticonvulsant activity, pregabalin is three to ten times more potent than gabapentin. Therefore,pregabalin can be used for the potential treatment of several central nervous system (CNS) disorders including epilepsy, neuropathic pain, anxiety and social phobia. Many synthetic routes have been developed to prepare pregabalin.2-3 However, there is a need to explore novel, practical and better synthetic approaches to pregabalin. Herein we report a concise synthesis of (±)-pregabalin from hydrolysis of corresponding (a)-lactam, which was obtained from the intramolecular C-H insertion of N-cumyl a-diazoacetamide 4.

  2. Novel method utilizing microbial treatment for cleaner production of diosgenin from Dioscorea zingiberensis C.H. Wright (DZW). (United States)

    Wei, Mi; Bai, Yun; Ao, Mingzhang; Jin, Wenwen; Yu, Panpan; Zhu, Min; Yu, Longjiang


    A novel method utilizing microbial treatment for cleaner production of diosgenin from Dioscorea zingiberensis C.H. Wright (DZW) was presented. A new Bacillus pumilus HR19, which has the great ability to secrete pectinase, was screened and applied in the microbial treatment. Low-pressure steam expansion pretreatment (LSEP) was employed in advance to assist microbial treatment efficiently in releasing saponins, which are the precursors of diosgenin. Compared with the traditional process of acid hydrolysis, this novel process reduced the consumptions of water, acid and organic solvent by more than 92.5%, 97.0%, 97.0%, respectively, while simultaneously increasing the diosgenin yield by 6.21%. In addition, the microbial treatment was more efficient than enzymatic treatment, which arised from that microorganisms could be induced to secrete related enzymes by the compositions of DZW and relieve product inhibition by utilizing enzyme hydrolysates.

  3. Modeling the absorption behavior of solar thermal collector coatings utilizing graded alpha-C:H/TiC layers. (United States)

    Gruber, D P; Engel, G; Sormann, H; Schüler, A; Papousek, W


    Wavelength selective coatings are of common use in order to enhance the efficiency of devices heated by radiation such as solar thermal collectors. The use of suitable materials and the optimization of coating layer thicknesses are advisable ways to maximize the absorption. Further improvement is achievable by embedding particles in certain layers in order to modify material properties. We focus on optimizing the absorption behavior of a solar collector setup using copper as substrate, a layer of amorphous hydrogenated carbon with embedded titanium carbide particles (a-C:H/TiC), and an antireflection coating of amorphous silicon dioxide (aSiO(2)). For the setup utilizing homogeneous particle distribution, a relative absorption of 90.98% was found, while inhomogeneous particle embedding yielded 98.29%. These results are particularly interesting since until now, absorption of more than 95% was found only by using embedded Cr but not by using the more biocompatible Ti.

  4. Cross-coupling of C(sp)-H Bonds with Organometallic Reagents via Pd(II)/Pd(0) Catalysis** (United States)

    Wasa, Masayuki; Engle, Keary M; Yu, Jin-Quan


    Palladium-catalyzed C-H activation/C-C bond-forming reactions have emerged as a promising class of synthetic tools in organic chemistry. Among the many different means of forging C-C bonds using Pd-mediated C-H activation, a new horizon in this field is Pd(II)-catalyzed cross-coupling of C-H bonds with organometallic reagents via a Pd(II)/Pd(0) catalytic cycle. While this type of reaction has proven to be effective for the selective functionalization of aryl C(sp(2))-H bonds, the focus of this review is on Pd(II)-catalyzed C(sp(3))-H activation/C-C cross-coupling, a topic of particular importance because reactions of this type enable fundamentally new methods for bond construction. Since our laboratory's initial report on cross-coupling of C-H bonds in 2006, this area has expanded rapidly, and the unique ability of Pd(II) catalysts to cleave and functionalize alkyl C(sp(3))-H bonds has been exploited to develop protocols for forming an array of C(sp(3))-C(sp(2)) and C(sp(3))-C(sp(3)) bonds. Furthermore, enantioselective C(sp(3))-H activation/C-C cross-coupling has been achieved through the use of chiral amino acid-derived ligands, offering a novel technique for producing enantioenriched molecules. Although this nascent field remains at an early stage of development, further investigations hold the potential to revolutionalize the way in which chiral molecules are synthesized in industrial and academic laboratories.

  5. Surface morphology and grain analysis of successively industrially grown amorphous hydrogenated carbon films (a-C:H) on silicon

    Energy Technology Data Exchange (ETDEWEB)

    Catena, Alberto [Department of Physics, University of Koblenz-Landau, 56070 Koblenz (Germany); McJunkin, Thomas [Department of Physics, The Ohio State University, 43210 Columbus, Ohio (United States); Agnello, Simonpietro; Gelardi, Franco M. [Department of Physics and Chemistry, University of Palermo, 90100 Palermo (Italy); Wehner, Stefan [Department of Physics, University of Koblenz-Landau, 56070 Koblenz (Germany); Fischer, Christian B., E-mail: [Department of Physics, University of Koblenz-Landau, 56070 Koblenz (Germany)


    Graphical abstract: - Highlights: • Two different a-C:H coatings in various thicknesses on Si (1 0 0) have been studied. • For both types no significant difference in surface morphology is detectable. • The grain number with respect to their height appears randomly distributed. • In average no grain higher than 14 nm and larger than 0.05 μm{sup 2} was observed. • A height to area correlation confines all detected grains to a limited region. - Abstract: Silicon (1 0 0) has been gradually covered by amorphous hydrogenated carbon (a-C:H) films via an industrial process. Two types of these diamond-like carbon (DLC) coatings, one more flexible (f-DLC) and one more robust (r-DLC), have been investigated. Both types have been grown by a radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique with acetylene plasma. Surface morphologies have been studied in detail by atomic force microscopy (AFM) and Raman spectroscopy has been used to investigate the DLC structure. Both types appeared to have very similar morphology and sp{sup 2} carbon arrangement. The average height and area for single grains have been analyzed for all depositions. A random distribution of grain heights was found for both types. The individual grain structures between the f- and r-type revealed differences: the shape for the f-DLC grains is steeper than for the r-DLC grains. By correlating the average grain heights to the average grain areas for all depositions a limited region is identified, suggesting a certain regularity during the DLC deposition mechanisms that confines both values. A growth of the sp{sup 2} carbon entities for high r-DLC depositions is revealed and connected to a structural rearrangement of carbon atom hybridizations and hydrogen content in the DLC structure.

  6. Monte Carlo techniques in radiation therapy

    CERN Document Server

    Verhaegen, Frank


    Modern cancer treatment relies on Monte Carlo simulations to help radiotherapists and clinical physicists better understand and compute radiation dose from imaging devices as well as exploit four-dimensional imaging data. With Monte Carlo-based treatment planning tools now available from commercial vendors, a complete transition to Monte Carlo-based dose calculation methods in radiotherapy could likely take place in the next decade. Monte Carlo Techniques in Radiation Therapy explores the use of Monte Carlo methods for modeling various features of internal and external radiation sources, including light ion beams. The book-the first of its kind-addresses applications of the Monte Carlo particle transport simulation technique in radiation therapy, mainly focusing on external beam radiotherapy and brachytherapy. It presents the mathematical and technical aspects of the methods in particle transport simulations. The book also discusses the modeling of medical linacs and other irradiation devices; issues specific...

  7. Multi-level quantum monte Carlo wave functions for complex reactions: The decomposition of α-hydroxy-dimethylnitrosamine

    NARCIS (Netherlands)

    Fracchia, F.; Filippi, C.; Amovilli, C.


    We present here several novel features of our recently proposed Jastrow linear generalized valence bond (J-LGVB) wave functions, which allow a consistently accurate description of complex potential energy surfaces (PES) of medium-large systems within quantum Monte Carlo (QMC). In particular, we deve

  8. In silico radiobiology: Have we reached the limit of Monte Carlo simulations? (United States)

    Gholami, Y.; Toghyani, M.; Champion, C.; Kuncic, Z.


    Monte Carlo radiation transport models are increasingly being used to simulate biological damage. However, such radiation biophysics simulations require realistic molecular models for water, whereas existing Monte Carlo models are limited by their use of atomic cross-sections, which become inadequate for accurately modelling interactions of the very low-energy electrons that are responsible for biological damage. In this study, we borrow theoretical methods commonly employed in molecular dynamics simulations to model the molecular wavefunction of the water molecule as the first step towards deriving new molecular cross-sections. We calculate electron charge distributions for molecular water and find non-negligible differences between the vapor and liquid phases that can be attributed to intermolecular bonding in the condensed phase. We propose that a hybrid Monte Carlo - Molecular Dynamics (MC-MD) approach to modelling radiation biophysics will provide new insights into radiation damage and new opportunities to develop targeted molecular therapy strategies.

  9. Approaching Chemical Accuracy with Quantum Monte Carlo


    Petruzielo, Frank R.; Toulouse, Julien; Umrigar, C. J.


    International audience; A quantum Monte Carlo study of the atomization energies for the G2 set of molecules is presented. Basis size dependence of diffusion Monte Carlo atomization energies is studied with a single determinant Slater-Jastrow trial wavefunction formed from Hartree-Fock orbitals. With the largest basis set, the mean absolute deviation from experimental atomization energies for the G2 set is 3.0 kcal/mol. Optimizing the orbitals within variational Monte Carlo improves the agreem...

  10. Mean field simulation for Monte Carlo integration

    CERN Document Server

    Del Moral, Pierre


    In the last three decades, there has been a dramatic increase in the use of interacting particle methods as a powerful tool in real-world applications of Monte Carlo simulation in computational physics, population biology, computer sciences, and statistical machine learning. Ideally suited to parallel and distributed computation, these advanced particle algorithms include nonlinear interacting jump diffusions; quantum, diffusion, and resampled Monte Carlo methods; Feynman-Kac particle models; genetic and evolutionary algorithms; sequential Monte Carlo methods; adaptive and interacting Marko

  11. Effect of ultrasonic power and bonding force on the bonding strength of copper ball bonds

    Institute of Scientific and Technical Information of China (English)


    Copper wire, serving as a cost-saving alternative to gold wire, has been used in many high-end thermosonic ball bonding applications. In this paper, the bond shear force, bond shear strength, and the ball bond diameter are adopted to evaluate the bonding quality. It is concluded that the efficient ultrasonic power is needed to soften the ball to form the copper bonds with high bonding strength. However, excessive ultrasonic power would serve as a fatigue loading to weaken the bonding. Excessive or less bonding force would cause cratering in the silicon.

  12. Path-integral Monte Carlo method for the local Z2 Berry phase. (United States)

    Motoyama, Yuichi; Todo, Synge


    We present a loop cluster algorithm Monte Carlo method for calculating the local Z(2) Berry phase of the quantum spin models. The Berry connection, which is given as the inner product of two ground states with different local twist angles, is expressed as a Monte Carlo average on the worldlines with fixed spin configurations at the imaginary-time boundaries. The "complex weight problem" caused by the local twist is solved by adopting the meron cluster algorithm. We present the results of simulation on the antiferromagnetic Heisenberg model on an out-of-phase bond-alternating ladder to demonstrate that our method successfully detects the change in the valence bond pattern at the quantum phase transition point. We also propose that the gauge-fixed local Berry connection can be an effective tool to estimate precisely the quantum critical point.

  13. Iridium-catalyzed [3 + 2] annulation of cyclic N-sulfonyl ketimines with 1,3-dienes via C-H activation. (United States)

    Nishimura, Takahiro; Ebe, Yusuke; Hayashi, Tamio


    Ir-catalyzed [3 + 2] annulation of cyclic N-sulfonyl ketimines with 1,3-dienes, in which an aryliridium intermediate is formed via C-H activation, gives aminoindane derivatives in high yields with high regio- and diastereoselectivity.

  14. Transversely Compressed Bonded Joints

    DEFF Research Database (Denmark)

    Hansen, Christian Skodborg; Schmidt, Jacob Wittrup; Stang, Henrik


    The load capacity of bonded joints can be increased if transverse pressure is applied at the interface. The transverse pressure is assumed to introduce a Coulomb-friction contribution to the cohesive law for the interface. Response and load capacity for a bonded single-lap joint was derived using...... non-linear fracture mechanics. The results indicated a good correlation between theory and tests. Furthermore, the model is suggested as theoretical base for determining load capacity of bonded anchorages with transverse pressure, in externally reinforced concrete structures....

  15. Metal-activated histidine carbon donor hydrogen bonds contribute to metalloprotein folding and function. (United States)

    Schmiedekamp, Ann; Nanda, Vikas


    Carbon donor hydrogen bonds are typically weak interactions that contribute less than 2 kcal/mol, and provide only modest stabilization in proteins. One exception is the class of hydrogen bonds donated by heterocyclic side chain carbons. Histidine is capable of particularly strong interactions through the Cepsilon(1) and Cdelta(2) carbons when the imidazole is protonated or bound to metal. Given the frequent occurrence of metal-bound histidines in metalloproteins, we characterized the energies of these interactions through DFT calculations on model compounds. Imidazole-water hydrogen bonding could vary from -11.0 to -17.0 kcal/mol, depending on the metal identity and oxidation state. A geometric search of metalloprotein structures in the PDB identified a number of candidate His C-H...O hydrogen bonds which may be important for folding or function. DFT calculations on model complexes of superoxide reductase show a carbon donor hydrogen bond positioning a water molecule above the active site.

  16. Monte Carlo Treatment Planning for Advanced Radiotherapy

    DEFF Research Database (Denmark)

    Cronholm, Rickard

    and validation of a Monte Carlo model of a medical linear accelerator (i), converting a CT scan of a patient to a Monte Carlo compliant phantom (ii) and translating the treatment plan parameters (including beam energy, angles of incidence, collimator settings etc) to a Monte Carlo input file (iii). A protocol...... previous algorithms since it uses delineations of structures in order to include and/or exclude certain media in various anatomical regions. This method has the potential to reduce anatomically irrelevant media assignment. In house MATLAB scripts translating the treatment plan parameters to Monte Carlo...


    Energy Technology Data Exchange (ETDEWEB)



    We present a new hybrid Monte Carlo method for 1-D equilibrium diffusion problems in which the radiation field coexists with matter in local thermodynamic equilibrium. This method, the Equilibrium Discrete Diffusion Monte Carlo (EqDDMC) method, combines Monte Carlo particles with spatially discrete diffusion solutions. We verify the EqDDMC method with computational results from three slab problems. The EqDDMC method represents an incremental step toward applying this hybrid methodology to non-equilibrium diffusion, where it could be simultaneously coupled to Monte Carlo transport.

  18. Combined effect of bond and potential disorder in half-doped manganites. (United States)

    Kumar, Sanjeev; Kampf, Arno P


    We analyze the effects of both bond and potential disorder in the vicinity of a first-order metal insulator transition in a two-band model for manganites using a real-space Monte Carlo method. Our results reveal a novel charge-ordered state coexisting with spin-glass behavior. We provide the basis for understanding the phase diagrams of half-doped manganites, and contrast the effects of bond and potential disorder and the combination of both.

  19. Spin-glass transition in Heisenberg spin system with ± J random bonds (United States)

    Ghazali, A.; Lallemand, P.; Diep, H. T.


    We investigate by Monte Carlo simulations the simple cubic lattice with Heisenberg spins interacting via short range ± J random bonds for different antiferromagnetic bond concentrations x. We find that for x<0.25, a transition of the para-ferromagnetic type occurs. For 0.25⪅ x⩽0.5, the existence of a remanant magnetization and of a rounded peak of the specific heat together with other data support a paramagnetic-spin-glass transition at finite temperature.

  20. Pd/Cu-catalyzed C-H arylation of 1,3,4-thiadiazoles with (hetero)aryl iodides, bromides, and triflates. (United States)

    Vachhani, Dipak D; Sharma, Abhishek; Van der Eycken, Erik


    The direct C-H arylation of 1,3,4-thiadiazoles with a wide range of (hetero)aryl iodides, bromides, and triflates is described using a Pd/Cu-catalyzed protocol. The methodology is compatible with substrates possessing electron-donating or electron-withdrawing substituents and also tolerates sterically hindered aryl halides. The utility of the developed protocol is demonstrated by a one-pot C-H arylation-Suzuki coupling sequence.