Sample records for catalytic c-h bond

  1. Enantioselective synthesis of a PKC inhibitor via catalytic C-H bond activation. (United States)

    Wilson, Rebecca M; Thalji, Reema K; Bergman, Robert G; Ellman, Jonathan A


    [reaction: see text] The syntheses of two biologically active molecules possessing dihydropyrroloindole cores (1 and 2) were completed using rhodium-catalyzed imine-directed C-H bond functionalization, with the second of these molecules containing a stereocenter that can be set with 90% ee during cyclization using chiral nonracemic phosphoramidite ligands. Catalytic decarbonylation and direct indole/maleimide coupling provide efficient access to 2.

  2. 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

  3. Salt-Free Strategy for the Insertion of CO2 into C-H Bonds: Catalytic Hydroxymethylation of Alkynes. (United States)

    Wendling, Timo; Risto, Eugen; Krause, Thilo; Gooßen, Lukas J


    A copper(I) catalyst enables the insertion of carbon dioxide into alkyne C-H bonds by using a suitable organic base with which hydrogenation of the resulting carboxylate salt with regeneration of the base becomes thermodynamically feasible. In the presence of catalytic copper(I) chloride/4,7-diphenyl-1,10-phenanthroline, polymer-bound triphenylphosphine, and 2,2,6,6-tetramethylpiperidine as the base, terminal alkynes undergo carboxylation at 15 bar CO 2 and room temperature. After filtration, the ammonium alkynecarboxylate can be hydrogenated to the primary alcohol and water at a rhodium/molybdenum catalyst, regenerating the amine base. This demonstrates the feasibility of a salt-free overall process, in which carbon dioxide serves as a C1 building block in a C-H functionalization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation (United States)

    Garrison Kinney, R.; Tjutrins, Jevgenijs; Torres, Gerardo M.; Liu, Nina Jiabao; Kulkarni, Omkar; Arndtsen, Bruce A.


    The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

  5. Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions (United States)

    Zhou, Tian

    Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the

  6. Isomerization of Internal Alkynes to Iridium(III) Allene Complexes via C-H Bond Activation: Expanded Substrate Scope, and Progress towards a Catalytic Methodology. (United States)

    Phadke, Neha; Findlater, Michael


    The synthesis of a series of allene complexes (POCOP)Ir(η²-RC=(.)=CR') 1b-4b (POCOP = 2,6-bis(di-tert-butylphosphonito)benzene) via isomerization of internal alkynes is reported. We have demonstrated that the application of this methodology is viable for the isomerization of a wide variety of alkyne substrates. Deuterium labeling experiments support our proposed mechanism. The structures of the allene complexes 1b-4b were determined using spectroscopic data analysis. Additionally, the solid-state molecular structure of complex 2b was determined using single crystal X-ray diffraction studies and it confirmed the assignment of an iridium-bound allene isomerization product. The rates of isomerization were measured using NMR techniques over a range of temperatures to allow determination of thermodynamic parameters. Finally, we report a preliminary step towards developing a catalytic methodology; the allene may be liberated from the metal center by exposure of the complex to an atmosphere of carbon monoxide.

  7. 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.

  8. Inert C-H Bond Transformations Enabled by Organometallic Manganese Catalysis. (United States)

    Hu, Yuanyuan; Zhou, Bingwei; Wang, Congyang


    Traditional organic synthesis relies heavily on the transformations of various preinstalled functional groups, such as cross-coupling reactions using organohalides and organometallic reagents. The strategy of C-H activation enables the direct formation of C-C/C-X (X = heteroatom) bonds from inert C-H bonds, which can enhance the atom- and step-economy of organic synthesis. To date, precious metals have overwhelmingly dominated the C-H activation field; however, the rarity and high cost of these metals necessitate the development of more sustainable catalysts. In this regard, catalysts based on manganese are highly desirable owing to the abundant reserve of manganese in the earth's crust and its economic benefits, low toxicity, and potentially unique reactivity. Although the first stoichiometric manganese-mediated C-H activation reaction was reported as early as 1970, manganese-catalyzed C-H activation reactions are largely underdeveloped. How to construct an efficient catalytic cycle for manganese in C-H activation reactions remains as a key issue to be addressed. In this Account, we summarize our recent advances in the manganese-catalyzed transformations of inert C-H bonds. To overcome the challenges associated with building manganese-based catalytic cycles, we developed two novel strategies, namely, synergy between manganese catalysts and bases and between manganese catalysts (with or w/o bases) and acids. By implementing the former strategy, we developed cooperative manganese/base catalytic systems that facilitate a new mode of C-H bond activation by manganese via a redox-neutral base-assisted deprotonation mechanism. As such, the requirement for the tedious preparation of MnR(CO) 5 complexes (R = Me, Bn, Ph) in stoichiometric reactions was eliminated, and a series of manganese-catalyzed C-H activation reactions of arenes with various reaction partners having C≡C and C═C bonds were achieved. Through the latter strategy of synergy between manganese catalysts

  9. Recent advances in C-S bond formation via C-H bond functionalization and decarboxylation. (United States)

    Shen, Chao; Zhang, Pengfei; Sun, Qiang; Bai, Shiqiang; Hor, T S Andy; Liu, Xiaogang


    The development of mild and general methods for C-S bond formation has received significant attention because the C-S bond is indispensable in many important biological and pharmaceutical compounds. Early examples for the synthesis of C-S bonds are generally limited to the condensation reaction between a metal thiolate and an organic halide. Recent chemical approaches for C-S bond formation, based upon direct C-H bond functionalization and decarboxylative reactions, not only provide new insights into the mechanistic understanding of C-S coupling reactions but also allow the synthesis of sulfur-containing compounds from more effective synthetic routes with high atom economy. This review intends to explore recent advances in C-S bond formation via C-H functionalization and decarboxylation, and the growing opportunities they present to the construction of complex chemical scaffolds for applications encompassing natural product synthesis, synthetic methodology development, and functional materials as well as nanotechnology.

  10. Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation. (United States)

    Gong, Liang; Xing, Li-Juan; Xu, Tong; Zhu, Xue-Ping; Zhou, Wen; Kang, Ning; Wang, Bin


    An oxidative olefination reaction between aliphatic primary amines and benzylic sp(3) C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration.

  11. Highly efficient and enantioselective cyclization of aromatic imines via directed C-H bond activation. (United States)

    Thalji, Reema K; Ellman, Jonathan A; Bergman, Robert G


    The first highly enantioselective catalytic reaction involving aromatic C-H bond activation is communicated. Enantioselective cyclization of aromatic ketimines containing alkenyl groups tethered at the meta position of an imine directing group has been achieved using 5 mol % [RhCl(coe)2]2 and 15 mol % of an (S)-binol-derived phosphoramidite ligand. Selectivities of up to 96% ee and up to quantitative yields were obtained. Moreover, the identified catalyst system enables the intramolecular alkylation reaction to be performed at temperatures 75 degrees C lower than our previously reported achiral system. The reaction can even be performed at room temperature for one of the optimal substrates.

  12. Origin of the Ability of α-Fe2 O3 Mesopores to Activate C-H Bonds in Methane. (United States)

    Dong, Bing; Han, Zhen; Zhang, Yongbo; Yu, Youyi; Kong, Aiguo; Shan, Yongkui


    Methane is a most abundant and inexpensive hydrocarbon feedstock for the production of chemicals and fuels. However, it is extremely difficult to directly convert methane to higher hydrocarbons because the C-H bonds in methane are the most stable C-H bonds of all hydrocarbons. The activation of the C-H bonds in methane by using an efficient and mild route remains a daunting challenge. Here, we show that the inner surface structures of the pore walls in mesoporous α-Fe 2 O 3 possess excellent catalytic performance for methane activation and convert C-H bonds into the C-O bonds in an O 2 atmosphere at 140 °C. We found that such unusual structures are mainly comprised of turbostratic ribbons and K crystal faces and have higher catalytic activity than the (110) plane. These results are without precedent in the history of catalysis chemistry and will provide a new pathway for designing and preparing highly efficient catalytic materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Activation of C-H bond in methane by Pd atom from the bonding evolution theory perspective. (United States)

    Nizovtsev, Anton S


    We report detailed study focused on the electron density redistribution during the simple oxidative addition reaction being the crucial stage of various catalytic processes. The bonding evolution theory based on the electron localization function and Thom's catastrophe theory shows that activation of methane's C-H bond by Pd atom consist of six elementary steps. The important feature revealed is the pronounced reorganization of Pd's outer core maxima corresponding to N-shell electrons of metal. Electronic rearrangements identified in this model reaction are likely to be the case in the more complex reactions of the same type involving transition metal compounds and, in principle, can be observed by modern ultrafast spectroscopy and diffraction techniques. Copyright © 2013 Wiley Periodicals, Inc.

  14. Designing Homogeneous Bromine Redox Catalysis for Selective Aliphatic C-H Bond Functionalization. (United States)

    Muniz, Kilian; Becker, Peter; Duhamel, Thomas; Martinez, Claudio


    The potential of homogeneous oxidation catalysis employing bromine has remained largely unexplored. The combination of tetraalkylammonium bromide and 3-chloroperbenzoic acid offers a unique catalyst system for the convenient and selective oxidation of saturated Csp3-H bonds upon photochemical initiation with visible light. It enables remote intramolecular, position-selective C-H amination as demonstrated for 20 different examples. For the first time, a N-halogenated intermediate could be isolated as the active catalyst state in a catalytic Hofmann-Löffler reaction. In addition, a novel expeditious one-pot synthesis of N-sulfonyloxaziridines from N-sulfonamides was developed and exemplified for 15 transformations. These pioneering examples provide a change in paradigm for molecular catalysis with bromine. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Observation of Weak C-H...O Hydrogen Bonding by Unactivated Alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xue B.; Woo, Hin-koon; Boggavarapu, Kiran; Wang, Lai S.


    Weak C-H...O hydrogen bonding has been recognized to play a major role in biological molecular structures and functions. A newly developed low-temperature photoelectron spectroscopy apparatus is used here to study the C-H...O hydrogen bonding between unactivated alkanes and the carboxylate functional group. We observed that gaseous linear carboxylates, CH3(CH2)nCO2-, assume folded structures at low temperatures due to weak C-H...O hydrogen bonding between the terminal CH3 and CO2- groups for n-5. Temperature-dependent studies showed that the folding transition depends on both the temperature and the aliphatic chain length. Theoretical calculations revealed that for n = 3-8, the folded conformations are more stable than the linear structures, but C-H...O hydrogen bonding only forms for species with n-5 due to steric constraint in the smaller species. One C-H...O hydrogen-bond is formed in the n = 5 and 6 species, whereas two C-H...O hydrogen-bonds are formed for n = 7 and 8. Comparison of the photoelectron spectral shifts for the folded relative to the linear conformations yielded lower limits for the strength of the C-H...O hydrogen-bonds in CH3(CH2)nCO2-, ranging from 1.2 kcal/mol for n = 5 to 4.4 kcal/mol for n = 8.

  16. Selective Palladium(II)-Catalyzed Carbonylation of Methylene β-C-H Bonds in Aliphatic Amines. (United States)

    Cabrera-Pardo, Jaime R; Trowbridge, Aaron; Nappi, Manuel; Ozaki, Kyohei; Gaunt, Matthew J


    Palladium(II)-catalyzed C-H carbonylation reactions of methylene C-H bonds in secondary aliphatic amines lead to the formation of trans-disubstituted β-lactams in excellent yields and selectivities. The generality of the C-H carbonylation process is aided by the action of xantphos-based ligands and is important in securing good yields for the β-lactam products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Mechanistic Investigations of C-H Activations on Silica-Supported Co(ii) Sites in Catalytic Propane Dehydrogenation. (United States)

    Estes, Deven P


    Catalytic reactions involving C-H bond activations are central to the chemical industry. One such example, alkane dehydrogenation, has recently become very important due to shortfalls in propene production and a large supply of cheap propane. However, current technologies are inefficient and have only moderate selectivity. In order to understand how to improve currently used catalysts, we must know more about the mechanism by which propane is dehydrogenated. We show here that Co(ii) sites on silica are good catalysts for the dehydrogenation of propane, having high activity and selectivity that is reasonably stable over the course of 10 h. Mechanistic investigations of this catalyst show that the main activation mechanism is most likely C-H activation by 1,2 addition.

  18. Pd-Catalyzed C-H Bond Functionalization on the Indole and Pyrrole Nucleus (United States)

    Beck, Elizabeth M.; Gaunt, Matthew J.

    This review details recent developments in the Pd-catalyzed C-H bond arylation and alkenylation of indoles and pyrroles, aromatic heterocycles that are frequently displayed in natural products and medicinal agents.

  19. Site-selective and stereoselective functionalization of non-activated tertiary C-H bonds (United States)

    Liao, Kuangbiao; Pickel, Thomas C.; Boyarskikh, Vyacheslav; Bacsa, John; Musaev, Djamaladdin G.; Davies, Huw M. L.


    The synthesis of complex organic compounds usually relies on controlling the reactions of the functional groups. In recent years, it has become possible to carry out reactions directly on the C-H bonds, previously considered to be unreactive. One of the major challenges is to control the site-selectivity because most organic compounds have many similar C-H bonds. The most well developed procedures so far rely on the use of substrate control, in which the substrate has one inherently more reactive C-H bond or contains a directing group or the reaction is conducted intramolecularly so that a specific C-H bond is favoured. A more versatile but more challenging approach is to use catalysts to control which site in the substrate is functionalized. p450 enzymes exhibit C-H oxidation site-selectivity, in which the enzyme scaffold causes a specific C-H bond to be functionalized by placing it close to the iron-oxo haem complex. Several studies have aimed to emulate this enzymatic site-selectivity with designed transition-metal catalysts but it is difficult to achieve exceptionally high levels of site-selectivity. Recently, we reported a dirhodium catalyst for the site-selective functionalization of the most accessible non-activated (that is, not next to a functional group) secondary C-H bonds by means of rhodium-carbene-induced C-H insertion. Here we describe another dirhodium catalyst that has a very different reactivity profile. Instead of the secondary C-H bond, the new catalyst is capable of precise site-selectivity at the most accessible tertiary C-H bonds. Using this catalyst, we modify several natural products, including steroids and a vitamin E derivative, indicating the applicability of this method of synthesis to the late-stage functionalization of complex molecules. These studies show it is possible to achieve site-selectivity at different positions within a substrate simply by selecting the appropriate catalyst. We hope that this work will inspire the design of

  20. Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate. (United States)

    Massena, Casey J; Riel, Asia Marie S; Neuhaus, George F; Decato, Daniel A; Berryman, Orion B


    (1)H NMR spectroscopic and X-ray crystallographic investigations of a 1,3-bis(4-ethynyl-3-iodopyridinium)benzene scaffold with perrhenate reveal strong halogen bonding in solution, and bidentate association in the solid state. A nearly isostructural host molecule demonstrates significant C-H hydrogen bonding to perrhenate in the same phases.

  1. Non-specificity of C-H bond rupture by γ radiolysis of 3-methylpentane glass

    International Nuclear Information System (INIS)

    Laet, M. de; Tilquin, B.


    Some authors using esr data claimed that there is a high selectivity for the rupture of a particular C-H bond after the radiolysis of solid branched alkanes. Using the identification of dimer isomers and very low total dose, we have established the identity of the trapped radical produced at 77 K by the radiolysis of 3-methylpentane, all the parent radicals are formed. If there is a different probability of breaking a particular C-H bond, the bond rupture is not much less selective in liquid than in the glassy state [fr

  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 ((CH 3 ) 2 PO 2 - ) have been prepared and tested in the alkoxycarbonylation of aromatic C-H bonds. The complex [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(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'-(CH 3 ) 2 PO 2 )(CO)L] 2 (L = PPh 3 , P(OMe)Ph 2 and P(OPh) 3 ) were obtained by carbonylation of the related mononuclear complexes [Rh(κO-(CH 3 ) 2 PO 2 )(cod)(L)], which were prepared in situ by the reaction of [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(cod)] 2 with 2 equivalents of L. Conversely, if L = IPr, the reaction of [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(CO)L] 2 with carbon monoxide affords the mononuclear complex [Rh(κO-(CH 3 ) 2 PO 2 )(CO) 2 IPr]. The subsequent reaction with trimethylamine N-oxide gives the corresponding binuclear complex [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(CO)(IPr)] 2 by abstraction of one of the carbonyl ligands. Complexes [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(cod)] 2 and [Rh(κO-(CH 3 ) 2 PO 2 )(cod)(L)] (L = IPr, PPh 3 , P(OMe)Ph 2 , 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'-(CH 3 ) 2 PO 2 )(CO) 2 ] 2 and [Rh(μ-Cl)(CO) 2 ] 2 , generated in situ from [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(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. 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}.

  5. 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.

  6. 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

  7. Cp*Rh(III)/Bicyclic Olefin Cocatalyzed C-H Bond Amidation by Intramolecular Amide Transfer. (United States)

    Wang, Xiaoming; Gensch, Tobias; Lerchen, Andreas; Daniliuc, Constantin G; Glorius, Frank


    A bicyclic olefin was discovered as a cocatalyst in a Cp*Rh(III)-catalyzed C-H bond amidation proceeding by an intramolecular amide transfer in N-phenoxyacetamide derivatives. Combining experimental and theoretical studies, we propose that the olefin promotes a Rh(III) intermediate to undergo oxidative addition into the O-N bond to form a Rh(V) nitrenoid species and subsequently direct the nitrenoid to add to the ortho position. The amide directing group plays a dual role as a cleavable coordinating moiety as well as an essential coupling partner for the C-H amidation. This methodology was successfully applied to the late-stage diversification of natural products and a marketed drug under mild conditions.

  8. Ruthenium-catalyzed C7 amidation of indoline C-H bonds with sulfonyl azides. (United States)

    Pan, Changduo; Abdukader, Ablimit; Han, Jie; Cheng, Yixiang; Zhu, Chengjian


    A ruthenium-catalyzed direct C7 amidation of indoline C-H bonds with sulfonyl azides was developed. This procedure allows the synthesis of a variety of 7-amino-substituted indolines, which are useful in pharmaceutical. The good functional tolerances, as well as the mild conditions, are prominent feature of this method. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Iodine-catalyzed sp³ C-H bond activation by selenium dioxide: synthesis of diindolylmethanes and di(3-indolyl)selanides. (United States)

    Naidu, P Seetham; Majumder, Swarup; Bhuyan, Pulak J


    An efficient reaction protocol was developed for the synthesis of several diindolylmethane derivatives via the [Formula: see text] C-H bond activation of aryl methyl ketones by [Formula: see text] and indoles in the presence of catalytic amounts of [Formula: see text] at 80 [Formula: see text] using dioxane as solvent. Unexpectedly, an interesting class of di(3-indolyl)selenide compounds was isolated when the reaction was carried out at room temperature.

  10. 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.

  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. Annulation of aromatic imines via directed C-H bond activation. (United States)

    Thalji, Reema K; Ahrendt, Kateri A; Bergman, Robert G; Ellman, Jonathan A


    A directed C-H bond activation approach to the synthesis of indans, tetralins, dihydrofurans, dihydroindoles, and other polycyclic aromatic compounds is presented. Cyclization of aromatic ketimines and aldimines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using (PPh3)3RhCl (Wilkinson's catalyst). The cyclization of a range of aromatic ketimines and aldimines provides bi- and tricyclic ring systems with good regioselectivity. Different ring sizes and substitution patterns can be accessed through the coupling of monosubstituted, 1,1- or 1,2-disubstituted, and trisubstituted alkenes bearing both electron-rich and electron-deficient functionality.

  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. Direct α-C-H bond functionalization of unprotected cyclic amines (United States)

    Chen, Weijie; Ma, Longle; Paul, Anirudra; Seidel, Daniel


    Cyclic amines are ubiquitous core structures of bioactive natural products and pharmaceutical drugs. Although the site-selective abstraction of C-H bonds is an attractive strategy for preparing valuable functionalized amines from their readily available parent heterocycles, this approach has largely been limited to substrates that require protection of the amine nitrogen atom. In addition, most methods rely on transition metals and are incompatible with the presence of amine N-H bonds. Here we introduce a protecting-group-free approach for the α-functionalization of cyclic secondary amines. An operationally simple one-pot procedure generates products via a process that involves intermolecular hydride transfer to generate an imine intermediate that is subsequently captured by a nucleophile, such as an alkyl or aryl lithium compound. Reactions are regioselective and stereospecific and enable the rapid preparation of bioactive amines, as exemplified by the facile synthesis of anabasine and (-)-solenopsin A.

  15. Selective C-H Bond Oxidation Catalyzed by the Fe-bTAML Complex: Mechanistic Implications. (United States)

    Ghosh, Munmun; Pattanayak, Santanu; Dhar, Basab B; Singh, Kundan K; Panda, Chakadola; Sen Gupta, Sayam


    Nonheme iron complexes bearing tetradentate N-atom-donor ligands with cis labile sites show great promise for chemoselective aliphatic C-H hydroxylation. However, several challenges still limit their widespread application. We report a mechanism-guided development of a peroxidase mimicking iron complex based on the bTAML macrocyclic ligand framework (Fe-bTAML: biuret-modified tetraamido macrocyclic ligand) as a catalyst to perform selective oxidation of unactivated 3° bonds with unprecedented regioselectivity (3°:2° of 110:1 for adamantane oxidation), high stereoretention (99%), and turnover numbers (TONs) up to 300 using mCPBA as the oxidant. Ligand decomposition pathways involving acid-induced demetalation were identified, and this led to the development of more robust and efficient Fe-bTAML complexes that catalyzed chemoselective C-H oxidation. Mechanistic studies, which include correlation of the product formed with the Fe V (O) reactive intermediates generated during the reaction, indicate that the major pathway involves the cleavage of C-H bonds by Fe V (O). When these oxidations were performed in the presence of air, the yield of the oxidized product doubled, but the stereoretention remained unchanged. On the basis of 18 O labeling and other mechanistic studies, we propose a mechanism that involves the dual activation of mCPBA and O 2 by Fe-bTAML, leading to formation of the Fe V (O) intermediate. This high-valent iron oxo remains the active intermediate for most of the reaction, resulting in high regio- and stereoselectivity during product formation.

  16. Molecular heterogeneous catalysts derived from bipyridine-based organosilica nanotubes for C-H bond activation. (United States)

    Zhang, Shengbo; Wang, Hua; Li, Mei; Han, Jinyu; Liu, Xiao; Gong, Jinlong


    Heterogeneous metal complex catalysts for direct C-H activation with high activity and durability have always been desired for transforming raw materials into feedstock chemicals. This study described the design and synthesis of one-dimensional organosilica nanotubes containing 2,2'-bipyridine (bpy) ligands in the framework (BPy-NT) and their post-synthetic metalation to provide highly active and robust molecular heterogeneous catalysts. By adjusting the ratios of organosilane precursors, very short BPy-NT with ∼50 nm length could be controllably obtained. The post-synthetic metalation of bipyridine-functionalized nanotubes with [IrCp*Cl(μ-Cl)] 2 (Cp* = η 5 -pentamethylcyclopentadienyl) and [Ir(cod)(OMe)] 2 (cod = 1,5-cyclooctadiene) afforded solid catalysts, IrCp*-BPy-NT and Ir(cod)-BPy-NT, which were utilized for C-H oxidation of heterocycles and cycloalkanes as well as C-H borylation of arenes. The cut-short nanotube catalysts displayed enhanced activities and durability as compared to the analogous homogeneous catalysts and other conventional heterogeneous catalysts, benefiting from the isolated active sites as well as the fast transport of substrates and products. After the reactions, a detailed characterization of Ir-immobilized BPy-NT via TEM, SEM, nitrogen adsorption, UV/vis, XPS, and 13 C CP MAS NMR indicated the molecular nature of the active species as well as stable structures of nanotube scaffolds. This study demonstrates the potential of BPy-NT with a short length as an integration platform for the construction of efficient heterogeneous catalytic systems for organic transformations.

  17. Cu-catalyzed cross-dehydrogenative coupling: A versatile strategy for C-C bond formations via the oxidative activation of sp3 C-H bonds (United States)

    Li, Zhiping; Bohle, D. Scott; Li, Chao-Jun


    Cu-catalyzed cross-dehydrogenative coupling (CDC) methodologies were developed based on the oxidative activation of sp3 C-H bonds adjacent to a nitrogen atom. Various sp, sp2, and sp3 C-H bonds of pronucleophiles were used in the Cu-catalyzed CDC reactions. Based on these results, the mechanisms of the CDC reactions also are discussed. C-H activation | catalysis | Baylis-Hillman reaction | Mannich reaction | Friedel-Crafts reaction

  18. Annulation of Aromatic Imines via Directed C-H BondActivation

    Energy Technology Data Exchange (ETDEWEB)

    Thalji, Reema K.; Ahrendt, Kateri A.; Bergman, Robert G.; Ellman,Jonathan A.


    A directed C-H bond activation approach to the synthesis of indans, tetralins, dihydrofurans, dihydroindoles, and other polycyclic aromatic compounds is presented. Cyclization of aromatic ketimines and aldimines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using (PPh{sub 3}){sub 3}RhCl (Wilkinson's catalyst). The cyclization of a range of aromatic ketimines and aldimines provides bi- and tricyclic ring systems with good regioselectivity. Different ring sizes and substitution patterns can be accessed through the coupling of monosubstituted, 1,1- or 1,2-disubstituted, and trisubstituted alkenes bearing both electron-rich and electron-deficient functionality.

  19. 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

  20. Enhancing Reactivity and Site-Selectivity in Hydrogen Atom Transfer from Amino Acid C-H Bonds via Deprotonation. (United States)

    Pipitone, Luca Maria; Carboni, Giulia; Sorrentino, Daniela; Galeotti, Marco; Salamone, Michela; Bietti, Massimo


    A kinetic study on the reactions of the cumyloxyl radical (CumO • ) with N-Boc-protected amino acids in the presence of the strong organic base DBU has been carried out. CO 2 H deprotonation increases the electron density at the α-C-H bonds activating these bonds toward HAT to the electrophilic CumO • strongly influencing the intramolecular selectivity. The implications of these results are discussed in the framework of HAT-based aliphatic C-H bond functionalization of amino acids and peptides.

  1. Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions. (United States)

    Corbin, Joshua R; Schomaker, Jennifer M


    Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

  2. Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination. (United States)

    Shin, Kwangmin; Kim, Hyunwoo; Chang, Sukbok


    Owing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon-nitrogen bonds. While metal-catalyzed C-N cross-coupling reactions have been established as one of the most general protocols for C-N bond formation, these methods require starting materials equipped with functional groups such as (hetero)aryl halides or their equivalents, thus generating stoichiometric amounts of halide salts as byproducts. To address this aspect, a transition-metal-catalyzed direct C-H amination approach has emerged as a step- and atom-economical alternative to the conventional C-N cross-coupling reactions. However, despite the significant recent advances in metal-mediated direct C-H amination reactions, most available procedures need harsh conditions requiring stoichiometric external oxidants. In this context, we were curious to see whether a transition-metal-catalyzed mild C-H amination protocol could be achieved using organic azides as the amino source. We envisaged that a dual role of organic azides as an environmentally benign amino source and also as an internal oxidant via N-N2 bond cleavage would be key to develop efficient C-H amination reactions employing azides. An additional advantage of this approach was anticipated: that a sole byproduct is molecular nitrogen (N2) under the perspective catalytic conditions. This Account mainly describes our research efforts on the development of rhodium- and iridium-catalyzed direct C-H amination reactions with organic azides. Under our initially optimized Rh(III)-catalyzed amination conditions, not only sulfonyl azides but also aryl- and alkyl azides could be utilized as facile amino sources in reaction with various types of C(sp(2))-H bonds bearing such directing groups as pyridine, amide, or ketoxime. More recently, a new

  3. 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.

  4. 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.

  5. Exclusive Aromatic vs Aliphatic C-H Bond Functionalization by Carbene Insertion with Gold-based Catalysts


    Rivilla de la Cruz, Iván; Gómez Emeterio, Bella Pilar; Romero Fructos-Vázquez, Manuel; Díaz Requejo, María Mar; Pérez Romero, Pedro José


    The direct functionalization of aromatic C-H bonds by carbene insertion from diazocompounds catalyzed by gold complexes with N-heterocyclic ligands is described. The reaction is completely selective toward the Csp2-H bonds, other Csp3-H bonds remaining unreacted. A study with a several NHC ligands in Au(I) and Au(III) complexes has been performed. A potential application in profen derivatives has also been developed DGI (CTQ2008-00042BQU and Consolider Ingenio 2010, Grant CSD2006-0003) and...

  6. Synthesis of Fluorine-Containing 6-Arylpurine Derivatives via Cp*Co(III)-Catalyzed C-H Bond Activation. (United States)

    Murakami, Nanami; Yoshida, Misaki; Yoshino, Tatsuhiko; Matsunaga, Shigeki


    Cp*Co(III)-catalyzed (Cp*=pentamethylcyclopentadienyl) C-H bond functionalization of 6-arylpurines using gem-difluoroalkenes and allyl fluorides is described. The reaction with gem-difluoroalkenes afforded monofluoroalkenes with high (Z)-selectivity, while the reaction with allyl fluorides led to C-H allylation in moderate (Z)-selectivity. Both reactions proceeded using a user-friendly single-component catalyst [Cp*Co(CH 3 CN) 3 ](SbF 6 ) 2 in fluorinated alcohol solvents without any additives. Robustness was also demonstrated by a preparative-scale reaction under air.

  7. 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 desired spin

  8. Intramolecular C-H Bond Activation through a Flexible Ester Linkage

    Czech Academy of Sciences Publication Activity Database

    Shaffer, Christopher; Schröder, Detlef; Gutz, Ch.; Lutzen, A.


    Roč. 51, č. 32 (2012), s. 8097-8100 ISSN 1433-7851 Grant - others:European Research Council(XE) AdG HORIZOMS Institutional support: RVO:61388963 Keywords : C-H activation * copper * gas phase * ion mobility * oxidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 13.734, year: 2012

  9. Activation of Propane C-H and C-C Bonds by Gas-Phase Pt Atom: A Theoretical Study

    Directory of Open Access Journals (Sweden)

    Chang-Wei Hu


    Full Text Available The reaction mechanism of the gas-phase Pt atom with C3H8 has been systematically investigated on the singlet and triplet potential energy surfaces at CCSD(T//BPW91/6-311++G(d, p, Lanl2dz level. Pt atom prefers the attack of primary over secondary C-H bonds in propane. For the Pt + C3H8 reaction, the major and minor reaction channels lead to PtC3H6 + H2 and PtCH2 + C2H6, respectively, whereas the possibility to form products PtC2H4 + CH4 is so small that it can be neglected. The minimal energy reaction pathway for the formation of PtC3H6 + H2, involving one spin inversion, prefers to start at the triplet state and afterward proceed along the singlet state. The optimal C-C bond cleavages are assigned to C-H bond activation as the first step, followed by cleavage of a C-C bond. The C-H insertion intermediates are kinetically favored over the C-C insertion intermediates. From C-C to C-H oxidative insertion, the lowering of activation barrier is mainly caused by the more stabilizing transition state interaction ΔEint, which is the actual interaction energy between the deformed reactants in the transition state.

  10. Vapour-induced solid-state C-H bond activation for the clean synthesis of an organopalladium biothiol sensor. (United States)

    Monas, Andrea; Užarević, Krunoslav; Halasz, Ivan; Kulcsár, Marina Juribašić; Ćurić, Manda


    Room-temperature accelerated aging in the solid state has been applied for atom- and energy-efficient activation of either one or two C-H bonds of azobenzene and methyl orange by palladium(ii) acetate. Organopalladium complexes are prepared in quantitative reactions without potentially harmful side products. Dicyclopalladated methyl orange is water-soluble and is a selective chromogenic biothiol sensor at physiologically-relevant micromolar concentrations in buffered aqueous media.

  11. Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C-H Bond Activation. (United States)

    Hu, Jundie; Guan, Mingyu; Han, Jian; Huang, Zhi-Bin; Shi, Da-Qing; Zhao, Yingsheng


    A highly regioselective palladium-catalyzed ester-directed ortho-olefination of phenyl acetic and propionic esters with olefins via C-H bond activation has been developed. A wide variety of phenyl acetic and propionic esters were tolerated in this transformation, affording the corresponding olefinated aromatic compounds. The ortho-olefination of heterocyclic acetic and propionic esters also took place smoothly giving the products in good yields, thus proving the potential utility of this protocol in synthetic chemistry.

  12. Aromatic C-H bond activation revealed by infrared multiphoton dissociation spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Jašíková, L.; Hanikýřová, E.; Schröder, Detlef; Roithová, J.


    Roč. 47, č. 4 (2012), s. 460-465 ISSN 1076-5174 Grant - others:GA ČR(CZ) GAP207/11/0338; Seventh Framework Program(XE) 226716 Institutional research plan: CEZ:AV0Z40550506 Keywords : C-H activation * density functional theory calculations * ion spectroscopy * metal oxides * rearrangements Subject RIV: CC - Organic Chemistry Impact factor: 3.214, year: 2012

  13. 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.

  14. Enantioselective intramolecular hydroarylation of alkenes via directed C-H bond activation. (United States)

    Harada, Hitoshi; Thalji, Reema K; Bergman, Robert G; Ellman, Jonathan A


    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)2]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.

  15. Selective Palladium(II)-Catalyzed Carbonylation of Methylene β-C-H Bonds in Aliphatic Amines.


    Cabrera-Pardo, Jaime R; Trowbridge, Aaron; Nappi, Manuel; Ozaki, Kyohei; Gaunt, Matthew James


    Pd(II)-catalyzed C–H carbonylation of methylene C–H bonds in secondary aliphatic amines leads to the formation trans-disubstituted β-lactams in excellent yields and selectivities. The generality of the C–H carbonylation process is aided by the action of xantphos-based ligands and is important in securing good yields of the β-lactam products. EPSRC (EP/100548X/1), ERC (ERC-STG-259711), Royal Society (Wolfson Award), Marie Curie Foundation and Herchel Smith Foundation.

  16. 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 CO 2 drive our efforts to discover ways of converting excess CO 2 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 CO 2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H - to CO 2 , rather than recombining with H + to liberate H 2 . Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO 2 . Of particular interest are the nitride- and carbide-containing clusters: [Fe 4 N(CO) 12 ] - and its derivatives and [Fe 4 C(CO) 12 ] 2- . In both aqueous and mixed solvent conditions, [Fe 4 N(CO) 12 ] - forms a reduced hydride intermediate, [H-Fe 4 N(CO) 12 ] - , through stepwise electron and proton transfers. This hydride selectively reacts with CO 2 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 [Fe 4 N(CO) 12 ] - facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO 2 ; only H 2 is observed in this case. In contrast, isoelectronic [Fe 4 C(CO) 12 ] 2- features a concerted proton-electron transfer mechanism to form [H-Fe 4 C(CO) 12 ] 2- , which is selective for H 2 production even in the presence of CO 2 , in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none

  17. Activation of the C-H bond in benzene in the presence of vanadium and titanium complexes

    International Nuclear Information System (INIS)

    Grigoryan, Eh.A.; D'yachkovskij, F.S.; Zhuk, S.Ya.; Papoyan, A.T.; Vyshinskaya, L.I.


    A multiple deuterium hydrogen exchange between benzene and deuterated ethylene and methanol in the presence of bis-cyclopentadienylvanadium (CPsub(d)V) and deuterium is found. The reaction is carried out in glass ampules at the temperature of 70 deg C pressure of 0.3-40.0 atm and CP 2 V catalyst concentrations of 0.007-0.035 mol/l during 80-100 hrs under conditions of constant mixing. It is shown that deuterium hydrogen exchange takes place between benzene and deuterium molecules, in the presence of V(2). The deuterium hydrogen exchange under experimental conditions is only possible as a result of activation of the C-H bond in benzene molecules in V coordination sphere and is considerably accelerated in the presence of ethylene

  18. Short hydrogen bonds in the catalytic mechanism of serine proteases

    Directory of Open Access Journals (Sweden)



    Full Text Available The survey of crystallographic data from the Protein Data Bank for 37 structures of trypsin and other serine proteases at a resolution of 0.78–1.28 Å revealed the presence of hydrogen bonds in the active site of the enzymes, which are formed between the catalytic histidine and aspartate residues and are on average 2.7 Å long. This is the typical bond length for normal hydrogen bonds. The geometric properties of the hydrogen bonds in the active site indicate that the H atom is not centered between the heteroatoms of the catalytic histidine and aspartate residues in the active site. Taken together, these findings exclude the possibility that short “low-barrier” hydrogen bonds are formed in the ground state structure of the active sites examined in this work. Some time ago, it was suggested by Cleland that the “low-barrier hydrogen bond” hypothesis is operative in the catalytic mechanism of serine proteases, and requires the presence of short hydrogen bonds around 2.4 Å long in the active site, with the H atom centered between the catalytic heteroatoms. The conclusions drawn from this work do not exclude the validity of the “low-barrier hydrogen bond” hypothesis at all, but they merely do not support it in this particular case, with this particular class of enzymes.

  19. Homolytic bond dissociation energies for C-H bonds adjacent to sulfur and aromatic moieties: The effects of substituents of C-H bond strengths of the benzylic positions in coal model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Alnajjar, M.S.; Franz, J.A. [Pacific Northwest Lab., Richland, WA (United States); Gleicher, G.J.; Truksa, S. [Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry; Bordwell, F.; Zhang, Xian-Man [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry


    Sulfur-containing compounds are precursors for thiyl radicals at coal liquefaction temperatures due to the weakness of The and S-S bonds. Thiyl radicals play important roles in hydrogen atom shuttling between benzylic positions and catalyze the cleavage and the formation of strong C-C bonds. Although many reactions of thiyl and other sulfur-containing radicals are qualitatively understood, the homolytic bond dissociation energies (EDE`s) and the thermochemistry associated with many key high molecular weight hydrocarbon and sulfur-containing organic structures important to coal is lacking because they are inappropriate for gas-phase techniques. The measurement of BDE`s has been proven to be difficult even in the simplest of molecules.

  20. Thiocarbamate-Directed Tandem Olefination-Intramolecular Sulfuration of Two Ortho C-H Bonds: Application to Synthesis of a COX-2 Inhibitor. (United States)

    Li, Wendong; Zhao, Yingwei; Mai, Shaoyu; Song, Qiuling


    A palladium-catalyzed dual ortho C-H bond activation of aryl thiocarbamates is developed. This tandem reaction initiates by thiocarbamate-directed ortho C-H palladation, which leads to favorable olefin insertion rather than reductive elimination. The oxidative Heck reaction followed by another C-H activation and sulfuration affords the dual-functionalized products. This reaction provides a concise route to the S,O,C multisubstituted benzene skeleton which could be successfully applied for the synthesis of a COX-2 inhibitor.

  1. Hydrogen spillover in Pt-single-walled carbon nanotube composites: formation of stable C-H bonds. (United States)

    Bhowmick, Ranadeep; Rajasekaran, Srivats; Friebel, Daniel; Beasley, Cara; Jiao, Liying; Ogasawara, Hirohito; Dai, Hongjie; Clemens, Bruce; Nilsson, Anders


    Using in situ electrical conductivity and ex situ X-ray photoelectron spectroscopy (XPS) measurements, we have examined how the hydrogen uptake of single-walled carbon nanotubes (SWNTs) is influenced by the addition of Pt nanoparticles. The conductivity of platinum-sputtered single-walled carbon nanotubes (Pt-SWNTs) during molecular hydrogen exposure decreased more rapidly than that of the corresponding pure SWNTs, which supports a hydrogenation mechanism facilitated by "spillover" of dissociated hydrogen from the Pt nanoparticles. C 1s XPS spectra indicate that the Pt-SWNTs store hydrogen by means of chemisorption, that is, covalent C-H bond formation: molecular hydrogen charging at elevated pressure (8.27 bar) and room temperature yielded Pt-SWNTs with up to 16 ± 1.5 at. % sp(3)-hybridized carbon atoms, which corresponds to a hydrogen-storage capacity of 1.2 wt % (excluding the weight of Pt nanoparticles). Pt-SWNTs prepared by the Langmuir-Blodgett (LB) technique exhibited the highest Pt/SWNT ratio and also the best hydrogen uptake. © 2011 American Chemical Society

  2. Quantification of the selective activation of C--H bonds in short chain alkanes: The reactivity of ethane, propane, isobutane, n-butane, and neopentane on Ir(111)

    International Nuclear Information System (INIS)

    Johnson, D.F.; Weinberg, W.H.


    The initial probabilities of precursor-mediated, dissociative chemisorption of the saturated hydrocarbons 13 C-labeled ethane, propane, isobutane, n-butane, and neopentane on the close-packed Ir(111) surface have been measured. The selective activation of primary (1 degree), secondary (2 degree), and tertiary (3 degree) C--H bonds has been quantified by examining the reactivities of the selectively deuterated isotopomers of propane, C 3 H 8 , CH 3 CD 2 CH 3 , and C 3 D 8 , and of isobutane, (CH 3 ) 3 CH, (CH 3 ) 3 CD, and (CD 3 ) 3 CH. With respect to the bottom of the physically adsorbed well for each hydrocarbon, the apparent C--H bond activation energies have been found to be 10.4±0.3 kcal/mol (ethane), 11.4±0.3 kcal/mol (propane), 11.5±0.3 kcal/mol (n-butane), 11.3±0.3 kcal/mol (i-butane), and 11.3±0.3 kcal/mol (neopentane). For all the alkanes examined, the ratios of the preexponential factors of the rate coefficients of reaction and desorption are 1x10 -2 . The C--D bond activation energies are higher than the corresponding C--H bond activation energies by 480 cal/mol (ethane), 630 cal/mol (propane), and 660 cal/mol (i-butane). By analyzing the primary kinetic isotope effects for the selectively deuterated isotopomers of propane and isobutane, the 2 degree C--H bond activation energy is found to be 310±160 cal/mol less than the 1 degree C--H bond activation energy on this surface, and similarly, 3 degree C--H bond cleavage is less by 80±70 cal/mol. The quantification of the branching ratios within the C--H bond activation channel for propane and isobutane on this surface shows that the formation of 1 degree-alkyl intermediates is, in general, favored over the formation of either 2 degree- or 3 degree-alkyl intermediates. (Abstract Truncated)

  3. 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.

  4. Infrared and Raman spectroscopy and quantum chemistry calculation studies of C-H...O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoate

    Czech Academy of Sciences Publication Activity Database

    Sato, H.; Dybal, Jiří; Murakami, R.; Noda, I.; Ozaki, Y.

    744-747, - (2005), s. 35-46 ISSN 0022-2860 R&D Projects: GA AV ČR IAA4050208 Keywords : infrared and Raman spectroscopy * quantum chemical calculation * C-H...O hydrogen bonding Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.440, year: 2005

  5. A Role for Pd(IV) in Catalytic Enantioselective C-H Functionalization with Monoprotected Amino Acid Ligands under Mild Conditions. (United States)

    Plata, R Erik; Hill, David E; Haines, Brandon E; Musaev, Djamaladdin G; Chu, Ling; Hickey, David P; Sigman, Matthew S; Yu, Jin-Quan; Blackmond, Donna G


    Kinetic and mechanistic studies of the desymmetrization of benzhydrylamine using Pd/monoprotected amino acid ligands (Pd/MPAA) via C-H functionalization with molecular iodine provide mechanistic insight into the rate-determining step and the oxidation state of Pd in the C-H functionalization step. Enantiomeric excess is strikingly insensitive to temperature from ambient temperature up to over 70 °C, and reaction rate is insensitive to the electronic characteristics of the ligand's benzoyl protecting group. The reaction is highly robust with no evidence of catalyst deactivation. Intriguingly, C-H bond breaking does not occur prior to the addition of I 2 to the reaction mixture. Electrochemical experiments demonstrate the viability of oxidative addition of I 2 to Pd(II). Together with 19 F NMR studies, these observations suggest that iodine oxidizes Pd prior to addition of the amine substrate. This work may lead to a better general understanding of the subtle variations in the reaction mechanisms for C-H functionalization reactions that may be extant for this ligand class depending on substrate, amino acid ligand and protecting group, and reaction conditions.

  6. Mechanistic Basis for Efficient, Site-Selective, Aerobic Catalytic Turnover in Pd-Catalyzed C-H Imidoylation of Heterocycle-Containing Molecules. (United States)

    Tereniak, Stephen J; Stahl, Shannon S


    A recently reported Pd-catalyzed method for oxidative imidoylation of C-H bonds exhibits unique features that have important implications for Pd-catalyzed aerobic oxidation catalysis: (1) The reaction tolerates heterocycles that commonly poison Pd catalysts. (2) The site selectivity of C-H activation is controlled by an N-methoxyamide group rather than a suitably positioned heterocycle. (3) A Pd 0 source, Pd 2 (dba) 3 (dba = dibenzylideneacetone), is superior to Pd(OAc) 2 as a precatalyst, and other Pd II sources are ineffective. (4) The reaction performs better with air, rather than pure O 2 . The present study elucidates the origin of these features. Kinetic, mechanistic, and in situ spectroscopic studies establish that Pd II -mediated C-H activation is the turnover-limiting step. The t BuNC substrate is shown to coordinate more strongly to Pd II than pyridine, thereby contributing to the lack of heterocycle catalyst poisoning. A well-defined Pd II -peroxo complex is a competent intermediate that promotes substrate coordination via proton-coupled ligand exchange. The effectiveness of this substrate coordination step correlates with the basicity of the anionic ligands coordinated to Pd II , and Pd 0 catalyst precursors are most effective because they selectively afford the Pd II -peroxo in situ. Finally, elevated O 2 pressures are shown to contribute to background oxidation of the isonitrile, thereby explaining the improved performance of reactions conducted with air rather than 1 atm O 2 . These collective results explain the unique features of the aerobic C-H imidoylation of N-methoxybenzamides and have important implications for other Pd-catalyzed aerobic C-H oxidation reactions.

  7. Rh2(II)-catalyzed intramolecular aliphatic C-H bond amination reactions using aryl azides as the N-atom source. (United States)

    Nguyen, Quyen; Sun, Ke; Driver, Tom G


    Rhodium(II) dicarboxylate complexes were discovered to catalyze the intramolecular amination of unactivated primary, secondary, or tertiary aliphatic C-H bonds using aryl azides as the N-atom precursor. While a strong electron-withdrawing group on the nitrogen atom is typically required to achieve this reaction, we found that both electron-rich and electron-poor aryl azides are efficient sources for the metal nitrene reactive intermediate. © 2012 American Chemical Society

  8. sp{sup 3} versus sp{sup 2} C-H bond activation chemistry of 2-picoline by Th(IV) and U(IV) metallocene complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kiplinger, Jaqueline L. [Los Alamos National Laboratory, Mail Stop J514, Los Alamos, NM 87545 (United States)], E-mail:; Scott, Brian L.; Schelter, Eric J. [Los Alamos National Laboratory, Mail Stop J514, Los Alamos, NM 87545 (United States); Pool Davis Tournear, Jaime A


    The thorium alkyl complex (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3}){sub 2} and 2-picoline react to give preferential sp{sup 3} C-H bond activation in the presence of a more reactive sp{sup 2} C-H bond, while the analogous uranium complex, (C{sub 5}Me{sub 5}){sub 2}U(CH{sub 3}){sub 2}, reacts with only the ortho 2-picoline sp{sup 2} C-H bond, as originally expected. Herein, we describe this competitive sp{sup 3} versus sp{sup 2} C-H bond activation chemistry with 2-picoline and (C{sub 5}Me{sub 5}){sub 2}An(CH{sub 3}){sub 2} (An = Th, U) and provide experimental observations that suggest different mechanistic reaction pathways are operative for the uranium and thorium complexes. We also report the X-ray crystal structures for the thorium picolyl complex, (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3})[{eta}{sup 2}-(N,C)-2-CH{sub 2}-NC{sub 5}H{sub 3}], and the {eta}{sup 2}-pyridyl complexes (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3})[{eta}{sup 2}-(N,C)-6-CH{sub 3}-NC{sub 5}H{sub 3}] and (C{sub 5}Me{sub 5}){sub 2}U(CH{sub 3})[{eta}{sup 2}-(N,C)-6-CH{sub 3}-NC{sub 5}H{sub 3}].

  9. Heterometallic Pd(II)-Ni(II) complexes with meso-substituted dibenzotetraaza[14]annulene: double C-H bond activation and formation of a rectangular tetradibenzotetraaza[14]annulene. (United States)

    Khaledi, Hamid; Olmstead, Marilyn M; Fukuda, Takamitsu; Ali, Hapipah Mohd


    Three isomeric 2[Pd(II)-Ni(II)] metal complexes, derived from indoleninyl meso-substituted dibenzotetraaza[14]annulene, were synthesized. The resulting dimers feature Ni···Ni or, alternatively, Ni···π interactions in staggered or slipped cofacial structures. A remarkable insertion of palladium into two different C-H bonds yielded a 4[Pd(II)-Ni(II)] rectangular complex with dimensions of 8.73 × 10.38 Å.

  10. Selective C-C and C-H bond activation/cleavage of pinene derivatives: synthesis of enantiopure cyclohexenone scaffolds and mechanistic insights. (United States)

    Masarwa, Ahmad; Weber, Manuel; Sarpong, Richmond


    The continued development of transition-metal-mediated C-C bond activation/cleavage methods would provide even more opportunities to implement novel synthetic strategies. We have explored the Rh(I)-catalyzed C-C activation of cyclobutanols resident in hydroxylated derivatives of pinene, which proceed in a complementary manner to the C-C bond cleavage that we have observed with many traditional electrophilic reagents. Mechanistic and computational studies have provided insight into the role of C-H bond activation in the stereochemical outcome of the Rh-catalyzed C-C bond activation process. Using this new approach, functionalized cyclohexenones that form the cores of natural products, including the spiroindicumides and phomactin A, have been accessed.

  11. 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

  12. Access to the meta position of arenes through transition metal catalysed C-H bond functionalisation: a focus on metals other than palladium. (United States)

    Mihai, Madalina T; Genov, Georgi R; Phipps, Robert J


    The elaboration of simple arenes in order to access more complex substitution patterns is a crucial endeavor for synthetic chemists, given the central role that aromatic rings play in all manner of important molecules. Classical methods are now routinely used alongside stoichiometric organometallic approaches and, most recently, transition metal catalysis in the range of methodologies that are available to elaborate arene C-H bonds. Regioselectivity is an important consideration when selecting a method and, of all those available, it is arguably those that target the meta position that are fewest in number. The rapid development of transition metal-catalysed C-H bond functionalisation over the last few decades has opened new possibilities for meta-selective C-H functionalisation through the diverse reactivity of transition metals and their compatibility with a wide range of directing groups. The pace of discovery of such processes has grown rapidly in the last five years in particular and it is the purpose of this review to examine these but in doing so to place the focus on metals other than palladium, the specific contributions of which have been very recently reviewed elsewhere. It is hoped this will serve to highlight to the reader the breadth of current strategies and mechanisms that have been used to tackle this challenge, which may inspire further progress in the field.

  13. Iridium(iii)-catalyzed regioselective direct arylation of sp(2) C-H bonds with diaryliodonium salts. (United States)

    Gao, Pan; Liu, Li; Shi, Zhuangzhi; Yuan, Yu


    A regioselective direct arylation of arenes and olefins at the ortho position is reported. The key to the high selectivity is the appropriate choice of diaryliodonium salts as the arylating reagent in the presence of a cationic iridium(iii) catalyst. The coordination of the metal with an oxygen atom or a nitrogen atom and subsequent C-H activation allows for direct arylation with coupling partners. This reaction proceeds under mild reaction conditions and with a high tolerance of various functional groups including many halide functional groups.

  14. Regioselective C2 Oxidative Olefination of Indoles and Pyrroles through Cationic Rhodium(III)-Catalyzed C-H Bond Activation. (United States)

    Li, Bin; Ma, Jianfeng; Xie, Weijia; Song, Haibin; Xu, Shansheng; Wang, Baiquan


    Be economic with your atoms! An efficient Rh-catalyzed oxidative olefination of indoles and pyrroles with broad substrate scope and tolerance is reported. The catalytic reaction proceeds with excellent regio- and stereoselectivity. The directing group N,N-dimethylcarbamoyl was crucial for the reaction and could be removed easily. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Assessment of the intermediacy of arylpalladium carboxylate complexes in the direct arylation of benzene: evidence for C-H bond cleavage by "ligandless" species. (United States)

    Tan, Yichen; Hartwig, John F


    Palladium-catalyzed direct arylations of benzene have been proposed to occur by the generation of a phosphine-ligated arylpalladium pivalate complex LPd(Ar)(OPiv) and reaction of this complex with benzene. We have isolated an example of the proposed intermediate and evaluated whether this complex does react with benzene to form the biaryl products of direct arylation. In contrast to the proposed mechanism, no biaryl product was formed from cleavage of the benzene C-H bond by LPd(Ar)(OPiv). However, reactions of LPd(Ar)(OPiv) with benzene and additives that displace or consume the phosphine ligand formed the arylated products in good yield, suggesting that a "ligandless" arylpalladium(II) carboxylate complex undergoes the C-H cleavage step. Consistent with this conclusion, we found that reactions catalyzed by Pd(OAc)(2) without a ligand occur faster than, and with comparable selectivities to, reactions catalyzed by Pd(OAc)(2) and a phosphine ligand.

  16. Enthalpy of formation of the cyclohexadienyl radical and the C-H bond enthalpy of 1,4-cyclohexadiene: an experimental and computational re-evaluation. (United States)

    Gao, Yide; DeYonker, Nathan J; Garrett, E Chauncey; Wilson, Angela K; Cundari, Thomas R; Marshall, Paul


    A quantitative understanding of the thermochemistry of cyclohexadienyl radical and 1,4-cyclohexadiene is beneficial for diverse areas of chemistry. Given the interest in these two species, it is surprising that more detailed thermodynamic data concerning the homolytic C-H bond enthalpies of such entities have not been forthcoming. We thus undertook an experimental and computational evaluation of (a) the enthalpy of formation of cyclohexadienyl radical (C(6)H(7)), (b) the homolytic C-H bond enthalpy of 1,4-cyclohexadiene (C(6)H(8)), and (c) the enthalpy of the addition of a hydrogen atom to benzene. Using laser photolysis experiments coupled with highly accurate ab initio quantum mechanical techniques, a newly recommended enthalpy of formation for C(6)H(7) is determined to be 208.0 +/- 3.9 kJ mol(-1), leading to a homolytic bond dissociation enthalpy of 321.7 +/- 2.9 kJ mol(-1), almost 9 kJ mol(-1) higher than previously determined enthalpies that used less certain experimental values for the C(6)H(7) enthalpy of formation.

  17. Catalytic and Atom-Economic Csp3 -Csp3 Bond Formation: Alkyl Tantalum Ureates for Hydroaminoalkylation. (United States)

    DiPucchio, Rebecca C; Roşca, Sorin-Claudiu; Schafer, Laurel L


    Atom-economic and regioselective Csp3 -Csp3 bond formation has been achieved by rapid C-H alkylation of unprotected secondary arylamines with unactivated alkenes. The combination of Ta(CH 2 SiMe 3 ) 3 Cl 2 , and a ureate N,O-chelating-ligand salt gives catalytic systems prepared in situ that can realize high yields of β-alkylated aniline derivatives from either terminal or internal alkene substrates. These new catalyst systems realize C-H alkylation in as little as one hour and for the first time a 1:1 stoichiometry of alkene and amine substrates results in high yielding syntheses of isolated amine products by simple filtration and concentration. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Dehydrogenation and C-H Bond Insertion of Propene: La(η^2-C_3H_4) and HLa(η^3-C_3H_5) (United States)

    Kumari, Sudesh; Yang, Dong-Sheng


    Dehydrogenation and C-H bond insertion are observed in the reaction of laser-ablated La atoms with propene (C_3H_6) in a pulsed molecular beam source. Several dehydrogenated and inserted products are identified by the time-of-flight mass spectrometry. La(C_3H_4) formed from H_2 elimination and HLa(C_3H_5) formed by C-H bond insertion are characterized by pulsed-field-ionization electron and ion spectroscopy, in combination with density functional theory. Two isomers of La(C_3H_4) are identified from 1,2- and 1,3-dehydrogenation. The adiabatic ionization energies of 1,2- and 1,3-dehydrogenated isomers are measured to be 40506(5) and 40941(5) Cm-1, respectively. For the inserted product HLa(C_3H_5), La atom is bound to the allyl radical in a three-fold binding mode (η^3). It is observed that the ionization energy of the HLa(η^3-C_3H_5) insertion complex (41130(5) Cm-1) is close to that of the 1,3-dehydrogented La(η^2-C_3H_4) species.

  19. Analysis of the reactivities of protein C-H bonds to H atom abstraction by OH radical. (United States)

    Scheiner, Steve; Kar, Tapas


    Ab initio and density functional theory calculations are used to monitor the process wherein a OH· radical is allowed to approach the various CH groups of a Leu dipeptide, with its CH(2)CH(CH(3))(2) side chain. After forming an encounter complex, the OH· abstracts the pertinent H atom, and the resulting HOH is then dissociated from the complex. The energy barriers for H· abstraction from the β, γ, and δ CH groups are all less than 8 kcal/mol, but a significantly higher barrier is computed for the C(α)H removal. This higher barrier is the result of the strong H-bonds formed in the encounter complex between the OH· and the NH and C═O groups of the peptide units that surround the C(α) atom. This low-energy complex represents a kinetic trap which raises the energy needed to surmount the ensuing H· transfer barrier.

  20. Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp2 and sp3 C-H Bonds (United States)

    Nadres, Enrico T.; Santos, Gerson Ivan Franco; Shabashov, Dmitry; Daugulis, Olafs


    The scope of palladium-catalyzed, auxiliary-assisted direct arylation and alkylation of sp2 and sp3 C-H bonds of amine and carboxylic acid derivatives has been investigated. The method employs a palladium acetate catalyst, substrate, aryl, alkyl, benzyl, or allyl halide, and inorganic base in t-amyl alcohol or water solvent at 100-140 °C. Aryl and alkyl iodides as well as benzyl and allyl bromides are competent reagents in this transformation. Picolinic acid auxiliary is used for amine γ-functionalization and 8-aminoquinoline auxiliary is used for carboxylic acid β-functionalization. Some optimization of base, additives, and solvent is required for achieving best results. PMID:24090404

  1. Scope and limitations of auxiliary-assisted, palladium-catalyzed arylation and alkylation of sp2 and sp3 C-H bonds. (United States)

    Nadres, Enrico T; Santos, Gerson Ivan Franco; Shabashov, Dmitry; Daugulis, Olafs


    The scope of palladium-catalyzed, auxiliary-assisted direct arylation and alkylation of sp(2) and sp(3) C-H bonds of amine and carboxylic acid derivatives has been investigated. The method employs a palladium acetate catalyst, substrate, aryl, alkyl, benzyl, or allyl halide, and inorganic base in tert-amyl alcohol or water solvent at 100-140 °C. Aryl and alkyl iodides as well as benzyl and allyl bromides are competent reagents in this transformation. The picolinic acid auxiliary is used for amine γ-functionalization, and the 8-aminoquinoline auxiliary is used for carboxylic acid β-functionalization. Some optimization of base, additives, and solvent is required for achieving best results.

  2. Rhodium-catalyzed C-H bond activation for the synthesis of quinonoid compounds: Significant Anti-Trypanosoma cruzi activities and electrochemical studies of functionalized quinones. (United States)

    Jardim, Guilherme A M; Silva, Thaissa L; Goulart, Marilia O F; de Simone, Carlos A; Barbosa, Juliana M C; Salomão, Kelly; de Castro, Solange L; Bower, John F; da Silva Júnior, Eufrânio N


    Thirty four halogen and selenium-containing quinones, synthesized by rhodium-catalyzed C-H bond activation and palladium-catalyzed cross-coupling reactions, were evaluated against bloodstream trypomastigotes of T. cruzi. We have identified fifteen compounds with IC 50 /24 h values of less than 2 μM. Electrochemical studies on A-ring functionalized naphthoquinones were also performed aiming to correlate redox properties with trypanocidal activity. For instance, (E)-5-styryl-1,4-naphthoquinone 59 and 5,8-diiodo-1,4-naphthoquinone 3, which are around fifty fold more active than the standard drug benznidazole, are potential derivatives for further investigation. These compounds represent powerful new agents useful in Chagas disease therapy. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  3. Effects of structure on alpha C-H bond enthalpies of amino acid residues: relevance to H transfers in enzyme mechanisms and in protein oxidation. (United States)

    Rauk, A; Yu, D; Taylor, J; Shustov, G V; Block, D A; Armstrong, D A


    The bond dissociation enthalpies (BDE) of all of the amino acid residues, modeled by HC(O)NHCH(R)C(O)NH(2) (PH(res)), were determined at the B3LYP/6-31G//B3LYP/6-31G level, coupled with isodesmic reactions. The results for neutral side chains with phi, psi angles approximately 180 degrees, approximately 180 degrees in ascending order, to an expected accuracy of +/-10 kJ mol(-)(1), are Asn 326; cystine 330; Asp 332; Gln 334; Trp 337; Arg 340; Lys 340; Met 343; His 344; Phe 344; Tyr 344; Leu 344; Ala 345; Cys 346; Ser 349; Gly 350; Ile 351; Val 352; Glu 354; Thr 357; Pro-cis 358; Pro-trans 369. BDEs calculated at the ROMP2/6-31G//B3LYP/6-31G level exhibit the same trends but are approximately 7 kJ mol(-)(1) higher. All BDEs are smaller than those of typical secondary or tertiary C-H bonds due to the phenomenon of captodative stabilization. The stabilization is reduced by changes in the phi,psi angles. As a result the BDEs increase by about 10 kJ mol(-)(1) in beta-sheet and 40 kJ mol(-)(1) in alpha-helical environments, respectively. In effect the alpha C-H BDEs can be "tuned" from about 345 to 400 kJ mol(-)(1) by adjusting the local environment. Some very significant effects of this are seen in the current literature on H-transfer processes in enzyme mechanisms and in oxidative damage to proteins. These observations are discussed in terms of the findings of the present study.

  4. [Ru(IV)(F20-TPP)Cl2] efficiently catalysed inter- and intra-molecular nitrene insertion into sp3 C-H bonds of hydrocarbons using phosphoryl azides as nitrene sources. (United States)

    Xiao, Wenbo; Wei, Jinhu; Zhou, Cong-Ying; Che, Chi-Ming


    [Ru(IV)(F20-TPP)Cl2][H2(F20-TPP) = meso-tetrakis(pentafluorophenyl)porphyrin] is an active catalyst for both inter- and intra-molecular nitrene insertion into sp(3) C-H bonds of hydrocarbons in good to high product yields using phosphoryl azides as nitrene sources.

  5. α 'agostic' assistance in Ziegler-Natta polymerization of olefins. Deuterium isotopic perturbation of stereochemistry indicating coordination of an α C-H bond in chain propagation

    International Nuclear Information System (INIS)

    Piers, W.E.; Bercaw, J.E.


    The well-defined, homogeneous Ziegler-Natta olefin polymerization systems that have been reported recently provide an unprecedented opportunity to investigate the mechanism of this important process. While a consensus appears to be developing that in all these systems the active catalysts are the 14-electron, d 0 (or d 0 f n ) metallocene alkyls, Cp 2 MR (M = lanthanide or group 3 transition metal) or [Cp 2 MR] + (M = group 4 transition metal), the mechanism for chain propagation and the geometry of the transition state for olefin insertion into the metal-carbon bond have not yet been unequivocally established. In a cleverly conceived experiment, Grubbs et al. probed for an α agostic interaction in the transition state for olefin insertion. Racemic 1-d 1 -5-hexenylchlorotitanocene was prepared and found to undergo AlCl 2 (CH 2 CH 3 )-induced cyclization to a mixture of cis- and trans-2-d 1 -cyclopentylmethyl stereoisomers. Any α agostic assistance in the insertion step is expected to favor the trans product (vide infra). Hydrolysis and 2 H NMR analysis of the resultant mixture of deuteriomethylcyclopentanes revealed a 1.00 ± 0.05 ratio of trans:cis products, arguing against an α agostic assisted insertion in their system, however. The scandium hydride, {(η 5 -C 5 Me 4 ) 2 SiMe 2 }Sc(PMe 3 )H ('OpSc(PMe 3 )H'), cleanly catalyzes the hydrocyclization of 1,5-hexadiene to methylcyclopentane. The authors have adapted this catalytic hydrocyclization reaction along the lines of the Grubbs experiment to probe for α agostic assistance with the scandium system

  6. Activation of the C-H bond: catalytic hydroxylation of hydrocarbons by new cobaltic alkylperoxydic complexes; selective and catalytic cycloalkane dehydrogenation in presence of uranium for hydrogen transfer

    International Nuclear Information System (INIS)

    Brazi, E.


    The aim of the thesis is to improve efficiency and selectivity of chemical reactions for alkane transformations. In the first part decomposition of hydroperoxides and hydrocarbon hydroxylation by cobalt complexes is studied. In the second part cycloalkanes are dehydrogenated into aromatics with a Pt catalyst, trapping hydrogen by uranium. Uranium hydride UH 3 can yield very pure hydrogen at reasonable temperature [fr

  7. Rhodium(III)-Catalyzed Imidoyl C-H Activation for Annulations to Azolopyrimidines. (United States)

    Halskov, Kim Søholm; Witten, Michael R; Hoang, Gia L; Mercado, Brandon Q; Ellman, Jonathan A


    Azolopyrimidines are efficiently prepared by direct imidoyl C-H bond activation. Annulations of N-azolo imines with sulfoxonium ylides and diazoketones under redox-neutral conditions and alkynes under oxidizing conditions provide products with various arrangements of nitrogen atoms and carbon substituents. We have also probed the mechanism of this first example of Rh(III)-catalyzed direct imidoyl C-H activation by structural characterization of a catalytically competent rhodacycle obtained after C-H activation and by kinetic isotope effects.

  8. 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.

  9. 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(sp 3 )-C(sp 2 ) coupling, there is a growing demand for C-H alkylation reactions, wherein sp 3 C-H bonds are replaced with sp 3 C-alkyl groups. Here we describe a polarity-match-based selective sp 3 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 sp 3 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.

  10. Conserved water-mediated H-bonding dynamics of catalytic Asn ...

    Indian Academy of Sciences (India)


    Extensive energy minimization and molecular dynamics simulation studies up to 2 ns on all the PDB and solvated structures clearly revealed the involvement of the H-bonding association of the two water molecules in fixing the orientation of the asparagine residue of the catalytic triad. From this study, it is suggested that ...

  11. Conserved water-mediated H-bonding dynamics of catalytic Asn ...

    Indian Academy of Sciences (India)


    [Nandi T K, Bairagya H R, Mukhopadhyay B P, Sekar K, Sukul D and Bera A K 2009 Conserved water-mediated H-bonding dynamics of catalytic. Asn 175 in plant thiol protease; J. Biosci. 34 27–34]. Keywords. Conserved water in molecular recognition; MD simulation; plant cysteine protease. Abbreviations used: CHASA ...

  12. 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.

  13. 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.

  14. Palladium-catalysed C-H activation of aliphatic amines to give strained nitrogen heterocycles (United States)

    McNally, Andrew; Haffemayer, Benjamin; Collins, Beatrice S. L.; Gaunt, Matthew J.


    The development of new chemical transformations based on catalytic functionalization of unactivated C-H bonds has the potential to simplify the synthesis of complex molecules dramatically. Transition metal catalysis has emerged as a powerful tool with which to convert these unreactive bonds into carbon-carbon and carbon-heteroatom bonds, but the selective transformation of aliphatic C-H bonds is still a challenge. The most successful approaches involve a `directing group', which positions the metal catalyst near a particular C-H bond, so that the C-H functionalization step occurs via cyclometallation. Most directed aliphatic C-H activation processes proceed through a five-membered-ring cyclometallated intermediate. Considering the number of new reactions that have arisen from such intermediates, it seems likely that identification of distinct cyclometallation pathways would lead to the development of other useful chemical transformations. Here we report a palladium-catalysed C-H bond activation mode that proceeds through a four-membered-ring cyclopalladation pathway. The chemistry described here leads to the selective transformation of a methyl group that is adjacent to an unprotected secondary amine into a synthetically versatile nitrogen heterocycle. The scope of this previously unknown bond disconnection is highlighted through the development of C-H amination and carbonylation processes, leading to the synthesis of aziridines and β-lactams (respectively), and is suggestive of a generic C-H functionalization platform that could simplify the synthesis of aliphatic secondary amines, a class of small molecules that are particularly important features of many pharmaceutical agents.

  15. 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.…

  16. Reversible conversion of valence-tautomeric copper metal-organic frameworks dependent single-crystal-to-single-crystal oxidation/reduction: a redox-switchable catalyst for C-H bonds activation reaction. (United States)

    Huang, Chao; Wu, Jie; Song, Chuanjun; Ding, Ran; Qiao, Yan; Hou, Hongwei; Chang, Junbiao; Fan, Yaoting


    Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like Cu(I) framework and a topologically equivalent neutral Cu(I)Cu(II) mixed-valent framework. The unique conversion behavior of the Cu(I) framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C-H bonds.

  17. 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

  18. Heptanuclear Fe5Cu2-Phenylgermsesquioxane containing 2,2'-Bipyridine: Synthesis, Structure, and Catalytic Activity in Oxidation of C-H Compounds. (United States)

    Bilyachenko, Alexey N; Khrustalev, Victor N; Zubavichus, Yan V; Shul'pina, Lidia S; Kulakova, Alena N; Bantreil, Xavier; Lamaty, Frédéric; Levitsky, Mikhail M; Gutsul, Evgeniy I; Shubina, Elena S; Shul'pin, Georgiy B


    A new representative of an unusual family of metallagermaniumsesquioxanes, namely the heterometallic cagelike phenylgermsesquioxane (PhGeO 2 ) 12 Cu 2 Fe 5 (O)OH(PhGe) 2 O 5 (bipy) 2 (2), was synthesized and structurally characterized. Fe(III) ions of the complex are coordinated by oxa ligands: (i) cyclic (PhGeO 2 ) 12 and acyclic (Ph 2 Ge 2 O 5 ) germoxanolates and (ii) O 2- and (iii) HO - moieties. In turn, Cu(II) ions are coordinated by both oxa (germoxanolates) and aza ligands (2,2'-bipyridines). This "hetero-type" of ligation gives in sum an attractive pagoda-like molecular architecture of the complex 2. Product 2 showed a high catalytic activity in the oxidation of alkanes to the corresponding alkyl hydroperoxides (in yields up to 30%) and alcohols (in yields up to 100%) and in the oxidative formation of benzamides from alcohols (catalyst loading down to 0.4 mol % in Cu/Fe).

  19. A low-barrier hydrogen bond mediates antibiotic resistance in a noncanonical catalytic triad (United States)


    One group of enzymes that confer resistance to aminoglycoside antibiotics through covalent modification belongs to the GCN5-related N-acetyltransferase (GNAT) superfamily. We show how a unique GNAT subfamily member uses a previously unidentified noncanonical catalytic triad, consisting of a glutamic acid, a histidine, and the antibiotic substrate itself, which acts as a nucleophile and attacks the acetyl donor molecule. Neutron diffraction studies allow for unambiguous identification of a low-barrier hydrogen bond, predicted in canonical catalytic triads to increase basicity of the histidine. This work highlights the role of this unique catalytic triad in mediating antibiotic resistance while providing new insights into the design of the next generation of aminoglycosides. PMID:29632894

  20. Moving to Sustainable Metals. Multifunctional Ligands in Catalytic, Outer Sphere C-H, N-H and O-H Activation

    Energy Technology Data Exchange (ETDEWEB)

    Crabtree, Robert [Yale Univ., New Haven, CT (United States)


    Much of our work during this grant period has emphasized green chemistry and sustainability. For example, we were able to convert glycerine, a waste byproduct of biodiesel production, into lactic acid, a compound with numerous applications, notably in the food and cosmetics industry, as well as being a source material for a biodegradable plastic. This work required a catalyst, that ceases to work after a certain lapse of time. We were able to identify the way in which this deactivation occurs by identifying some of the metal catalyst deactivation products. These proved to be multimetallic clusters containing up to six metals and up to 14 hydrogen atoms. Both the catalytic reaction itself and the deactivation structures are novel and unexpected. We have previously proposed that nitrogen heterocycles could be good energy carriers in a low CO2 future world. In another part of our study, we found catalysts for introduction of hydrogen, an energy carrier that is hard to store, into nitrogen heterocycles. The mechanism of this process proved to be unusual in that the catalyst transfers the H2 to the heterocycle in the form of H+ and H-, first transferring the H+ and only then the H-. In a third area of study, some of our compounds, originally prepared for DOE catalysis purposes, also proved useful in hydrocarbon oxidation and in water oxidation. The latter is important in solar-to-fuel work, because, by analogy with natural photosynthesis, the goal of the Yale Solar Group of four PIs is to convert sunlight to hydrogen and oxygen, which requires water splitting catalysts. The catalysts that proved useful mediate the latter reaction: water oxidation to oxygen. In a more technical study, we developed methods for distinguishing the case where catalysis is mediated by a soluble catalyst from cases where catalysis arises from a deposit of finely divided solid. One particular application involved electrocatalysis

  1. A hydrogen-bonding network plays a catalytic role in photosynthetic oxygen evolution (United States)

    Polander, Brandon C.; Barry, Bridgette A.


    In photosystem II, oxygen evolution occurs by the accumulation of photo-induced oxidizing equivalents at the oxygen-evolving complex (OEC). The sequentially oxidized states are called the S0-S4 states, and the dark stable state is S1. Hydrogen bonds to water form a network around the OEC; this network is predicted to involve multiple peptide carbonyl groups. In this work, we tested the idea that a network of hydrogen bonded water molecules plays a catalytic role in water oxidation. As probes, we used OEC peptide carbonyl frequencies, the substrate-based inhibitor, ammonia, and the sugar, trehalose. Reaction-induced FT-IR spectroscopy was used to describe the protein dynamics associated with the S1 to S2 transition. A shift in an amide CO vibrational frequency (1664 (S1) to 1653 (S2) cm-1) was observed, consistent with an increase in hydrogen bond strength when the OEC is oxidized. Treatment with ammonia/ammonium altered these CO vibrational frequencies. The ammonia-induced spectral changes are attributed to alterations in hydrogen bonding, when ammonia/ammonium is incorporated into the OEC hydrogen bond network. The ammonia-induced changes in CO frequency were reversed or blocked when trehalose was substituted for sucrose. This trehalose effect is attributed to a displacement of ammonia molecules from the hydrogen bond network. These results imply that ammonia, and by extension water, participate in a catalytically essential hydrogen bond network, which involves OEC peptide CO groups. Comparison to the ammonia transporter, AmtB, reveals structural similarities with the bound water network in the OEC. PMID:22474345

  2. Characterization of the sp sup 2 bonds network in a-C:H layers with nuclear magnetic resonance, electron energy loss spectroscopy and electron spin resonance

    Energy Technology Data Exchange (ETDEWEB)

    Kleber, R.; Jung, K.; Ehrhardt, H. (Fachbereich Physik, Univ. Kaiserslautern (Germany)); Muehling, I.; Breuer, K. (Technische Univ. Chemnitz, Sektion Physik/Elektronische Bauelemente (Germany)); Metz, H.; Engelke, F. (Karl-Marx-Univ., Sektion Physik, Leipzig (Germany))


    a-C:H layers prepared at different ion energies have been investigated by several methods including {sup 13}C nuclear magnetic resonance (NMR), electron energy loss spectroscopy (EELS) and electron spin resonance (ESR). The sp{sup 2} fraction of the samples rose from 27% to about 60 at.% with increasing ion energies from 30 eV to 170 eV. In the EELS spectra of these layers the intensity of the {pi}{yields}{pi}{sup *} transition between 4 and 7 eV showed no significant variation. But a shift of the peak is observed from 7 eV to lower energy losses with increasing ion energies indicating an enhanced formation of larger sp{sup 2} cluster sizes. This shift is accompanied by a broadening of the energy loss peak, suggesting a broadening of the cluster size distribution. The ESR spectra showed an increase of the spin density by more than one order of magnitude with increasing ion energies. Simultaneously the linewidth of the ESR signal gets narrower. This can also be interpreted as an increasing cluster size from single benzene rings to three and four fused six-fold rings. Hence, the EELS and ESR spectra lead to the same conclusions with respect to the microstructure of the a-C:H network. (orig.).

  3. 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.

  4. Palladium-catalysed electrophilic aromatic C-H fluorination (United States)

    Yamamoto, Kumiko; Li, Jiakun; Garber, Jeffrey A. O.; Rolfes, Julian D.; Boursalian, Gregory B.; Borghs, Jannik C.; Genicot, Christophe; Jacq, Jérôme; van Gastel, Maurice; Neese, Frank; Ritter, Tobias


    Aryl fluorides are widely used in the pharmaceutical and agrochemical industries, and recent advances have enabled their synthesis through the conversion of various functional groups. However, there is a lack of general methods for direct aromatic carbon-hydrogen (C-H) fluorination. Conventional methods require the use of either strong fluorinating reagents, which are often unselective and difficult to handle, such as elemental fluorine, or less reactive reagents that attack only the most activated arenes, which reduces the substrate scope. A method for the direct fluorination of aromatic C-H bonds could facilitate access to fluorinated derivatives of functional molecules that would otherwise be difficult to produce. For example, drug candidates with improved properties, such as increased metabolic stability or better blood-brain-barrier penetration, may become available. Here we describe an approach to catalysis and the resulting development of an undirected, palladium-catalysed method for aromatic C-H fluorination using mild electrophilic fluorinating reagents. The reaction involves a mode of catalysis that is unusual in aromatic C-H functionalization because no organometallic intermediate is formed; instead, a reactive transition-metal-fluoride electrophile is generated catalytically for the fluorination of arenes that do not otherwise react with mild fluorinating reagents. The scope and functional-group tolerance of this reaction could provide access to functional fluorinated molecules in pharmaceutical and agrochemical development that would otherwise not be readily accessible.

  5. Gas-phase C-H and N-H bond activation by a high valent nitrido-iron dication and {NH}-transfer to activated olefins

    Czech Academy of Sciences Publication Activity Database

    Schlangen, M.; Neugebauer, J.; Reiher, M.; Schröder, Detlef; López, J. P.; Haryono, M.; Heinemann, F. W.; Grohmann, A.; Schwarz, H.


    Roč. 130, č. 13 (2008), s. 4285-4294 ISSN 0002-7863 R&D Projects: GA AV ČR KJB400550704 Grant - others:DFG(DE) SFB658 Institutional research plan: CEZ:AV0Z40550506 Keywords : azides * bond activation * dications * iron * mass spectrometry * metal nitrenes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.091, year: 2008

  6. A new face of phenalenyl-based radicals in the transition metal-free C-H arylation of heteroarenes at room temperature: trapping the radical initiatorviaC-C σ-bond formation. (United States)

    Ahmed, Jasimuddin; P, Sreejyothi; Vijaykumar, Gonela; Jose, Anex; Raj, Manthan; Mandal, Swadhin K


    The radical-mediated transition metal-free approach for the direct C-H bond functionalization of arenes is considered as a cost effective alternative to transition metal-based catalysis. An organic ligand-based radical plays a key role by generating an aryl radical which undergoes a subsequent functionalization process. The design principle of the present study takes advantage of a relatively stable odd alternant hydrocarbon-based phenalenyl (PLY) radical. In this study, the first transition metal-free catalyzed direct C-H arylation of a variety of heteroarenes such as azoles, furan, thiophene and pyridine at room temperature has been reported using a phenalenyl-based radical without employing any photoactivation step. This protocol has been successfully applied to the gram scale synthesis of core moieties of bioactive molecules. The phenalenyl-based radical initiator has been characterized crystallographically by trapping it via the formation of a C-C σ-bond between the phenalenyl radical and solvent-based radical species.

  7. Toluene and Ethylbenzene Aliphatic C-H Bond Oxidations Initiated by a Dicopper(II)-μ-1,2-Peroxo Complex (United States)

    Lucas, Heather R.; Li, Lei; Sarjeant, Amy A. Narducci; Vance, Michael A.; Solomon, Edward I.; Karlin, Kenneth D.


    With an anisole containing polypyridylamine potential tetradentate ligand OL, a μ-1,2-peroxo-dicopper(II) complex [{OLCuII}2(O22-)]2+ forms from the reaction of the mononuclear compound [CuI(OL)(MeCN)]B(C6F5)4(OLCuI) with O2 in non-coordinating solvents at -80 °C. Thermal decay of this peroxo complex in the presence of toluene or ethylbenzene leads to rarely seen C-H activation chemistry; benzaldehyde and acetophenone/1-phenylethanol mixtures, respectively, are formed. Experiments with 18O2 confirm that the oxygen source in the products is molecular O2 and deuterium labeling experiments indicate kH/kD = 7.5 ± 1 for the toluene oxygenation. The O2-reaction of [CuI(BzL)(CH3CN)]+ (BzLCuI) leads to a dicopper(III)-bis-μ-oxo species [{BzLCuIII}2(μ-O2-)2]2+ at -80 °C and from such solutions, very similar toluene oxygenation chemistry occurs. Ligand BzL is a tridentate chelate, possessing the same moiety found in OL, but without the anisole O-atom donor. In these contexts, the nature of the oxidant species in or derived from [{OLCuII}2(O22-)]2+ is discussed and likely mechanisms of reaction initiated by toluene H-atom abstraction chemistry are detailed. To confirm the structural formulations of the dioxygen-adducts, UV-vis and resonance Raman spectroscopic studies have been carried out and these results are reported and compared to previously described systems including [{CuII(PYL)}2(O2)]2+ (PYL =TMPA = tris(2-methylpyridyl)amine). Using (L)CuI, CO-binding properties (i.e., νC-O values) along with electrochemical property comparisons, the relative donor abilities of OL, BzL and PYL are assessed. PMID:19216527

  8. A meta-selective C-H borylation directed by a secondary interaction between ligand and substrate (United States)

    Kuninobu, Yoichiro; Ida, Haruka; Nishi, Mitsumi; Kanai, Motomu


    Regioselective C-H bond transformations are potentially the most efficient method for the synthesis of organic molecules. However, the presence of many C-H bonds in organic molecules and the high activation barrier for these reactions make these transformations difficult. Directing groups in the reaction substrate are often used to control regioselectivity, which has been especially successful for the ortho-selective functionalization of aromatic substrates. Here, we describe an iridium-catalysed meta-selective C-H borylation of aromatic compounds using a newly designed catalytic system. The bipyridine-derived ligand that binds iridium contains a pendant urea moiety. A secondary interaction between this urea and a hydrogen-bond acceptor in the substrate places the iridium in close proximity to the meta-C-H bond and thus controls the regioselectivity. 1H NMR studies and control experiments support the participation of hydrogen bonds in inducing regioselectivity. Reversible direction of the catalyst through hydrogen bonds is a versatile concept for regioselective C-H transformations.

  9. 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.

  10. Nickel-Catalyzed C-H Silylation of Arenes with Vinylsilanes: Rapid and Reversible β-Si Elimination. (United States)

    Elsby, Matthew R; Johnson, Samuel A


    The reaction of C 6 F 5 H and H 2 C═CHSiMe 3 with catalytic [ i Pr 2 Im]Ni(η 2 -H 2 C═CHSiMe 3 ) 2 (1b) exclusively forms the C-H silylation product C 6 F 5 SiMe 3 with ethylene as a byproduct ([ i Pr 2 Im] = 1,3-di(isopropyl)imidazole-2-ylidene). Catalytic C-H bond silylation is facile with partially fluorinated aromatic substrates containing two ortho fluorine substituents adjacent to the C-H bond and 1,2,3,4-tetrafluorobenzene. Less fluorinated substrates react slower. Under the same reaction conditions, catalytic [IPr]Ni(η 2 -H 2 C═CHSiMe 3 ) 2 (1a) ([IPr] = 1,3-bis[2,6-diisopropylphenyl]-1,3-dihydro-2H-imidazol-2-ylidene) provided only the alkene hydroarylation product C 6 F 5 CH 2 CH 2 SiMe 3 . Mechanistic studies reveal that the C-H activation and β-Si elimination steps are reversible under catalytic conditions with both catalysts 1a and 1b. With catalytic 1a, reversible ethylene loss after β-Si elimination was also observed despite its inability to catalyze C-H silylation; the reductive elimination step to form the silylation product is much slower than reductive elimination to form the alkene hydroarylation product. Reversible ethylene loss was not observed with 1b, which suggests that the rate-limiting step in the reaction is neither C-H activation nor β-Si elimination but either ethylene loss or reductive elimination of cis-disposed aryl and SiMe 3 moieties.

  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. Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

    Directory of Open Access Journals (Sweden)

    Matthieu Jouffroy


    Full Text Available The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon–carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2.

  13. Catalytic

    Directory of Open Access Journals (Sweden)

    S.A. Hanafi


    Full Text Available A series of dealuminated Y-zeolites impregnated by 0.5 wt% Pt catalysts promoted by different amounts of Ni, Pd or Cr (0.3 and 0.6 wt% were prepared and characterized as hydrocracking catalysts. The physicochemical and structural characterization of the solid catalysts were investigated and reported through N2 physisorption, XRD, TGA-DSC, FT-IR and TEM techniques. Solid catalysts surface acidities were investigated through FT-IR spectroscopy aided by pyridine adsorption. The solid catalytic activities were evaluated through hydroconversion of n-hexane and n-heptane employing micro-catalytic pulse technique directly connected to a gas chromatograph analyzer. The thermal stability of the solids was also investigated up to 800 °C. Crystallinity studies using the XRD technique of all modified samples proved analogous to the parent Y-zeolite, exhibiting nearly an amorphous and microcrystalline character of the second metal oxides. Disclosure of bimetallic catalysts crystalline characterization, through XRD, was not viable. The nitrogen adsorption–desorption isotherms for all samples concluded type I adsorption isotherms, without any hysteresis loop, indicating that the entire pore system is composed of micropores. TEM micrographs of the solid catalysts demonstrate well-dispersed Pt, Ni and Cr nanoparticles having sizes of 2–4 nm and 7–8 nm, respectively. The catalytic activity results indicate that the bimetallic (0.5Pt–0.3Cr/D18H–Y catalyst is the most active towards n-hexane and n-heptane isomerization while (0.5Pt–0.6Ni/D18H–Y catalyst can be designed as most suitable as a cracking catalyst.

  14. A conserved hydrogen-bond network in the catalytic centre of animal glutaminyl cyclases is critical for catalysis. (United States)

    Huang, Kai-Fa; Wang, Yu-Ruei; Chang, En-Cheng; Chou, Tsung-Lin; Wang, Andrew H-J


    QCs (glutaminyl cyclases; glutaminyl-peptide cyclotransferases, EC catalyse N-terminal pyroglutamate formation in numerous bioactive peptides and proteins. The enzymes were reported to be involved in several pathological conditions such as amyloidotic disease, osteoporosis, rheumatoid arthritis and melanoma. The crystal structure of human QC revealed an unusual H-bond (hydrogen-bond) network in the active site, formed by several highly conserved residues (Ser(160), Glu(201), Asp(248), Asp(305) and His(319)), within which Glu(201) and Asp(248) were found to bind to substrate. In the present study we combined steady-state enzyme kinetic and X-ray structural analyses of 11 single-mutation human QCs to investigate the roles of the H-bond network in catalysis. Our results showed that disrupting one or both of the central H-bonds, i.e., Glu(201)...Asp(305) and Asp(248)...Asp(305), reduced the steady-state catalysis dramatically. The roles of these two COOH...COOH bonds on catalysis could be partly replaced by COOH...water bonds, but not by COOH...CONH(2) bonds, reminiscent of the low-barrier Asp...Asp H-bond in the active site of pepsin-like aspartic peptidases. Mutations on Asp(305), a residue located at the centre of the H-bond network, raised the K(m) value of the enzyme by 4.4-19-fold, but decreased the k(cat) value by 79-2842-fold, indicating that Asp(305) primarily plays a catalytic role. In addition, results from mutational studies on Ser(160) and His(319) suggest that these two residues might help to stabilize the conformations of Asp(248) and Asp(305) respectively. These data allow us to propose an essential proton transfer between Glu(201), Asp(305) and Asp(248) during the catalysis by animal QCs.

  15. Ligand-enabled ortho-C-H olefination of phenylacetic amides with unactivated alkenes. (United States)

    Lu, Ming-Zhu; Chen, Xing-Rong; Xu, Hui; Dai, Hui-Xiong; Yu, Jin-Quan


    Although chelation-assisted C-H olefination has been intensely investigated, Pd(ii)-catalyzed C-H olefination reactions are largely restricted to acrylates and styrenes. Here we report a quinoline-derived ligand that enables the Pd(ii)-catalyzed olefination of the C(sp 2 )-H bond with simple aliphatic alkenes using a weakly coordinating monodentate amide auxiliary. Oxygen is used as the terminal oxidant with catalytic copper as the co-oxidant. A variety of functional groups in the aliphatic alkenes are tolerated. Upon hydrogenation, the ortho -alkylated product can be accessed. The utility of this reaction is also demonstrated by the late-stage diversification of drug molecules.

  16. Rhodium(0) metalloradicals in binuclear C-H activation

    NARCIS (Netherlands)

    Puschmann, F.F.; Grützmacher, H.; de Bruin, B.


    A reactive rhodium(0) metalloradical capable of binuclear activation of an aromatic C-H bond of PPh3 is disclosed. Kinetic measurements and density functional theory calculations reveal a binuclear mechanism: two metalloradicals add to a 'double bond' of the aromatic substrate while approaching the

  17. Reliability Tests of Aluminium Wedge Wire Bonding on Auto-catalytic Silver Immersion Gold (ASIG) PCB Metallization

    CERN Document Server

    Drozd, A; Kaufmann, S; Manolescu, F; McGill, I


    The Auto-catalytic Silver Immersion Gold (ASIG) PCB metallization is a new process that has clear advantages for PCB assembly especially with regard to lead-free soldering. As it may become a popular process in the future for electronics used in physics experiments, the quality of this metallization for aluminium wire bonding has been studied. Aluminium wedge wire bonding continues to be the interconnection method of choice for many physics detector sensors, for high density signal routing and for unpackaged die. Although advertised as having good quality for aluminium wire bonding, this study was performed to verify this claim as well as to test the longer term reliability of the wire bonds taking into consideration the environmental conditions and life-expectancy of devices, in particular for high energy physics detector applications. The tests were performed on PCBs made with the ASIG and ENIG (Electro-less Nickel Immersion Gold) processes at the same time in order to make a comparison with the current ind...

  18. Enzyme-controlled nitrogen-atom transfer enables regiodivergent C-H amination. (United States)

    Hyster, Todd K; Farwell, Christopher C; Buller, Andrew R; McIntosh, John A; Arnold, Frances H


    We recently demonstrated that variants of cytochrome P450BM3 (CYP102A1) catalyze the insertion of nitrogen species into benzylic C-H bonds to form new C-N bonds. An outstanding challenge in the field of C-H amination is catalyst-controlled regioselectivity. Here, we report two engineered variants of P450BM3 that provide divergent regioselectivity for C-H amination-one favoring amination of benzylic C-H bonds and the other favoring homo-benzylic C-H bonds. The two variants provide nearly identical kinetic isotope effect values (2.8-3.0), suggesting that C-H abstraction is rate-limiting. The 2.66-Å crystal structure of the most active enzyme suggests that the engineered active site can preorganize the substrate for reactivity. We hypothesize that the enzyme controls regioselectivity through localization of a single C-H bond close to the iron nitrenoid.

  19. The labeling of unsaturated gamma-hydroxybutyric acid by heavy isotopes of hydrogen: iridium complex-mediated H/D exchange by C-H bond activation vs reduction by boro-deuterides/tritides

    Czech Academy of Sciences Publication Activity Database

    Marek, Aleš; Pedersen, M. H. F.; Vogensen, S. B.; Clausen, R. P.; Frolund, B.; Elbert, Tomáš


    Roč. 59, č. 12 (2016), s. 476-483 ISSN 0362-4803 Institutional support: RVO:61388963 Keywords : C-H activation * borotritides * hydrogen/deuterium exchange * iridium catalyst * tritium-labeled gamma-hydroxybutyric acid Subject RIV: CC - Organic Chemistry Impact factor: 1.745, year: 2016

  20. Catalytic C-C Bond Cleavage for the Production of Chemicals from Lignin

    NARCIS (Netherlands)

    Jastrzebski, R.


    Lignin is a major component of lignocellulosic biomass and could be an important renewable feedstock in industry for the production of (aromatic) bulk and fine chemicals. To this end, the development of new catalytic processes is required; both to depolymerise the biopolymer into small aromatic

  1. Practical catalytic arylation of C–H bonds by iron/phenanthroline systems

    NARCIS (Netherlands)

    Huang, Y.


    In Chapter 1, an overview is given of the current status of the field of non-precious metal catalyzed/mediated direct arylation reactions. Reports on direct arylations catalyzed by Fe, Co, Ni and Cu are mainly demonstrated and discussed. Chapter 2 described a pre-made iron-based catalytic system

  2. Conformation-induced remote meta-C-H activation of amines (United States)

    Tang, Ri-Yuan; Li, Gang; Yu, Jin-Quan


    Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a long-standing challenge in organic chemistry. The small differences in intrinsic reactivity of C-H bonds in any given organic molecule can lead to the activation of undesired C-H bonds by a non-selective catalyst. One solution to this problem is to distinguish C-H bonds on the basis of their location in the molecule relative to a specific functional group. In this context, the activation of C-H bonds five or six bonds away from a functional group by cyclometallation has been extensively studied. However, the directed activation of C-H bonds that are distal to (more than six bonds away) functional groups has remained challenging, especially when the target C-H bond is geometrically inaccessible to directed metallation owing to the ring strain encountered in cyclometallation. Here we report a recyclable template that directs the olefination and acetoxylation of distal meta-C-H bonds--as far as 11 bonds away--of anilines and benzylic amines. This template is able to direct the meta-selective C-H functionalization of bicyclic heterocycles via a highly strained, tricyclic-cyclophane-like palladated intermediate. X-ray and nuclear magnetic resonance studies reveal that the conformational biases induced by a single fluorine substitution in the template can be enhanced by using a ligand to switch from ortho- to meta-selectivity.

  3. Importance of the oxygen bond strength for catalytic activity in soot oxidation

    DEFF Research Database (Denmark)

    Christensen, Jakob M.; Grunwaldt, Jan-Dierk; Jensen, Anker D.


    energies for soot oxidation follow linear Brønsted-Evans-Polanyi relationships with the heat of oxygen chemisorption. Among the tested metal or metal oxide catalysts Co3O4 and CeO2 were nearest to the optimal bond strength in tight contact oxidation, while Cr2O3 was nearest to the optimum in loose contact......The oxygen bond strength on a catalyst, as measured by the heat of oxygen chemisorption, is observed to be a very important parameter for the activity of the catalyst in soot oxidation. With both intimate contact between soot and catalyst (tight contact) and with the solids stirred loosely together...... oxidation. The optimum of the volcano curve in loose contact is estimated to occur between the bond strengths of α-Fe2O3 and α-Cr2O3. Guided by an interpolation principle FeaCrbOx binary oxides were tested, and the activity of these oxides was observed to pass through an optimum for an FeCr2Ox binary oxide...

  4. Thermal Shock Resistance of Si3N4/h -BN Composites Prepared via Catalytic Reaction-Bonding Route (United States)

    Yang, Wanli; Peng, Zhigang; Dai, Lina; Shi, Zhongqi; Jin, Zhihao


    Si3N4/h-BN ceramic matrix composites were prepared via a catalytic reaction-bonding route by using ZrO2 as nitridation catalyst, and the water quenching (fast cooling) and molten aluminum quenching tests (fast heating) were carried out to evaluate the thermal shock resistance of the composites. The results showed that the thermal shock resistance was improved obviously with the increase in h-BN content, and the critical thermal shock temperature difference (Δ T c) reaches as high as 780 °C when the h-BN content was 30 wt.%. The improvement of thermal shock resistance of the composites was mainly due to the crack tending to quasi static propagating at weak bonding interface between Si3N4 and h-BN with the increase in h-BN content. For the molten aluminum quenching test, the residual strength showed no obvious decrease compared with water quenching test, which could be caused by the mild stress condition on the surface. In addition, a calculated parameter, volumetric crack density ( N f), was presented to quantitative evaluating the thermal shock resistance of the composites in contrast to the conventional R parameter.

  5. (NHC)Cu-Catalyzed Mild C-H Amidation of (Hetero)arenes with Deprotectable Carbamates: Scope and Mechanistic Studies. (United States)

    Xie, Weilong; Yoon, Jung Hee; Chang, Sukbok


    Primary arylamines are an important unit broadly found in synthetic, biological, and materials science. Herein we describe the development of a (NHC)Cu system that mediates a direct C-H amidation of (hetero)arenes by using N-chlorocarbamates or their sodio derivatives as the practical amino sources. A facile stoichiometric reaction of reactive copper-aryl intermediates with the amidating reagent led us to isolate key copper arylcarbamate species with the formation of a C-N bond. The use of (t)BuONa base made this transformation catalytic under mild conditions. The present (NHC)Cu-catalyzed C-H amidation works efficiently and selectively on a large scale over a range of arenes including polyfluorobenzenes, azoles, and quinoline N-oxides. Deprotection of the newly installed carbamate groups such as Boc and Cbz was readily performed to afford the corresponding primary arylamines.

  6. Identification and H(D)-bond energies of C-H(D)Cl interactions in chloride-haloalkane clusters: a combined X-ray crystallographic, spectroscopic, and theoretical study. (United States)

    Serebryanskaya, Tatiyana V; Novikov, Alexander S; Gushchin, Pavel V; Haukka, Matti; Asfin, Ruslan E; Tolstoy, Peter M; Kukushkin, Vadim Yu


    The cationic (1,3,5-triazapentadiene)Pt(II) complex [Pt{NH[double bond, length as m-dash]C(N(CH2)5)N(Ph)C(NH2)[double bond, length as m-dash]NPh}2]Cl2 ([]Cl2) was crystallized from four haloalkane solvents giving [][Cl2(CDCl3)4], [][Cl2(CHBr3)4], [][Cl2(CH2Cl2)2], and [][Cl2(C2H4Cl2)2] solvates that were studied by X-ray diffraction. In the crystal structures of [][Cl2(CDCl3)4] and [][Cl2(CHBr3)4], the Cl(-) ion interacts with two haloform molecules via C-DCl(-) and C-HCl(-) contacts, thus forming the negatively charged isostructural clusters [Cl(CDCl3)2](-) and [Cl(CHBr3)2](-). In the structures of [][Cl2(CH2Cl2)2] and [][Cl2(C2H4Cl2)2], cations [](2+) are linked to a 3D-network by a system of H-bondings including one formed by each Cl(-) ion with CH2Cl2 or C2H4Cl2 molecules. The lengths and energies of these H-bonds in the chloride-haloalkane clusters were analyzed by DFT calculations (M06 functional) including AIM analysis. The crystal packing noticeably affected the geometry of the clusters, and energy of C-HCl(-) hydrogen bonds ranged from 1 to 6 kcal mol(-1). An exponential correlation (R(2) > 0.98) between the calculated Cl(-)H distances and the energies of the corresponding contacts was found and used to calculate hydrogen bond energies from the experimental Cl(-)H distances. Predicted energy values (3.3-3.9 kcal mol(-1) for the [Cl(CHCl3)2](-) cluster) are in a reasonable agreement with the energy of the Cl3C-HCl(-) bond estimated using ATRFTIR spectroscopy (2.7 kcal mol(-1)).

  7. Enantioselective Synthesis of a PKC Inhibitor via Catalytic C-HBond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Rebecca M.; Thalji, Reema K.; Bergman, Robert G.; Ellman,Jonathan A.


    The syntheses of two biologically active molecules possessing dihydropyrroloindole cores (1 and 2) were completed using rhodium-catalyzed imine-directed C-H bond functionalization, with the second of these molecules containing a stereocenter that can be set with 90% ee during cyclization using chiral nonracemic phosphoramidite ligands. Catalytic decarbonylation and direct indole/maleimide coupling provide efficient access to 2.

  8. Enzyme catalysis: C-H activation is a Reiske business (United States)

    Bruner, Steven D.


    Enzymes that selectively oxidize unactivated C-H bonds are capable of constructing complex molecules with high efficiency. A new member of this enzyme family is RedG, a Reiske-type oxygenase that catalyses chemically challenging cyclizations in the biosynthesis of prodiginine natural products.

  9. 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.

  10. S,O-Ligand-Promoted Palladium-Catalyzed C-H Functionalization Reactions of Nondirected Arenes

    NARCIS (Netherlands)

    Naksomboon, K.; Valderas, C.; Gomez-Martinez, M.; Alvarez-Casao, Y.; Fernández Ibáñez, M.A.

    Pd(II)-catalyzed C-H functionalization of non directed arenes has been realized using an inexpensive and easily accessible type of bidentate S,O-ligand. The catalytic system shows high efficiency in the C-H olefination reaction of electron-rich and electron-poor arenes. This methodology is

  11. First-Row Late Transition Metals for Catalytic Alkene Hydrofunctionalisation: Recent Advances in C-N, C-O and C-P Bond Formation

    Directory of Open Access Journals (Sweden)

    Sophie Bezzenine-Lafollée


    Full Text Available This review provides an outline of the most noteworthy achievements in the area of C-N, C-O and C-P bond formation by hydroamination, hydroalkoxylation, hydrophosphination, hydrophosphonylation or hydrophosphinylation reaction on unactivated alkenes (including 1,2- and 1,3-dienes promoted by first-row late transition metal catalytic systems based on manganese, iron, cobalt, nickel, copper and zinc. The relevant literature from 2009 until mid-2017 has been covered.

  12. Catalytic constructive deoxygenation of lignin-derived phenols: new C-C bond formation processes from imidazole-sulfonates and ether cleavage reactions. (United States)

    Leckie, Stuart M; Harkness, Gavin J; Clarke, Matthew L


    As part of a programme aimed at exploiting lignin as a chemical feedstock for less oxygenated fine chemicals, several catalytic C-C bond forming reactions utilising guaiacol imidazole sulfonate are demonstrated. These include the cross-coupling of a Grignard, a non-toxic cyanide source, a benzoxazole, and nitromethane. A modified Meyers reaction is used to accomplish a second constructive deoxygenation on a benzoxazole functionalised anisole.

  13. Comparative reactivity of TpRu(L)(NCMe)Ph (L = CO or PMe3): impact of ancillary ligand l on activation of carbon-hydrogen bonds including catalytic hydroarylation and hydrovinylation/oligomerization of ethylene. (United States)

    Foley, Nicholas A; Lail, Marty; Lee, John P; Gunnoe, T Brent; Cundari, Thomas R; Petersen, Jeffrey L


    Complexes of the type TpRu(L)(NCMe)R [L = CO or PMe3; R = Ph or Me; Tp = hydridotris(pyrazolyl)borate] initiate C-H activation of benzene. Kinetic studies, isotopic labeling, and other experimental evidence suggest that the mechanism of benzene C-H activation involves reversible dissociation of acetonitrile, reversible benzene coordination, and rate-determining C-H activation of coordinated benzene. TpRu(PMe3)(NCMe)Ph initiates C-D activation of C6D6 at rates that are approximately 2-3 times more rapid than that for TpRu(CO)(NCMe)Ph (depending on substrate concentration); however, the catalytic hydrophenylation of ethylene using TpRu(PMe3)(NCMe)Ph is substantially less efficient than catalysis with TpRu(CO)(NCMe)Ph. For TpRu(PMe3)(NCMe)Ph, C-H activation of ethylene, to ultimately produce TpRu(PMe3)(eta3-C4H7), is found to kinetically compete with catalytic ethylene hydrophenylation. In THF solutions containing ethylene, TpRu(PMe3)(NCMe)Ph and TpRu(CO)(NCMe)Ph separately convert to TpRu(L)(eta3-C4H7) (L = PMe3 or CO, respectively) via initial Ru-mediated ethylene C-H activation. Heating mesitylene solutions of TpRu(L)(eta3-C4H7) under ethylene pressure results in the catalytic production of butenes (i.e., ethylene hydrovinylation) and hexenes.

  14. C-H activation on platinum, a mechanistic study

    International Nuclear Information System (INIS)

    Lebrilla, C.B.; Maier, W.F.


    C-H activation on heterogeneous Pt catalysts is found to be most facile at low Pt dispersion and surface structure insensitive at dispersions above 10%. Two distinct processes have been identified which lead to the formation of mono- and polydeuterated products, respectively. The ratio of mono-/polydeuteration processes increases with increasing dispersion. Evidence is provided for the formation of π-intermediates as the initiator of polydeuteration. The most facile mechanism of exchange propagation in a single molecule is through a π-allyl-type interconversion. The deuterium in monodeuterated n-hexane is located at the terminal position by high-resolution deuterium NMR. NMR spectroscopy also provides evidence for steric effects which prevent significant H/D exchange at positions close to quaternary centers. C-H activation appears to be sensitive to steric hindrance, the C-H bond energy, and the partial pressure of the substrate

  15. Ag1 Pd1 Nanoparticles-Reduced Graphene Oxide as a Highly Efficient and Recyclable Catalyst for Direct Aryl C-H Olefination. (United States)

    Hu, Qiyan; Liu, Xiaowang; Wang, Guoliang; Wang, Feifan; Li, Qian; Zhang, Wu


    The efficient and selective palladium-catalyzed activation of C-H bonds is of great importance for the construction of diverse bioactive molecules. Despite significant progress, the inability to recycle palladium catalysts and the need for additives impedes the practical applications of these reactions. Ag 1 Pd 1 nanoparticles-reduced graphene oxide (Ag 1 Pd 1 -rGO) was used as highly efficient and recyclable catalyst for the chelation-assisted ortho C-H bond olefination of amides with acrylates in good yields with a broad substrate scope. The catalyst can be recovered and reused at least 5 times without losing activity. A synergistic effect between the Ag and Pd atoms on the catalytic activity was found, and a plausible mechanism for the AgPd-rGO catalyzed C-H olefination is proposed. These findings suggest that the search for such Pd-based bimetallic alloy nanoparticles is a new method towards the development of superior recyclable catalysts for direct aryl C-H functionalization under mild conditions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. C-H and H-H Activation in Transition Metal Complexes and on Surfaces. (United States)


    48) increases the *-xz overlap greatly. M-H becomes bonding, and :* significantly populated. The COOP curve shows increasing improvement in M-Ha...Activation, catalysis 20. ABSTRACT ’ Continuo an reverse od@ It necesary And Identily by Weeck num11ber) - .The breaking of the H-H bond in 142 and a C-H bond

  17. Ligand-controlled, tunable silver-catalyzed C-H amination. (United States)

    Alderson, Juliet M; Phelps, Alicia M; Scamp, Ryan J; Dolan, Nicholas S; Schomaker, Jennifer M


    The development of readily tunable and regioselective C-H functionalization reactions that operate solely through catalyst control remains a challenge in modern organic synthesis. Herein, we report that simple silver catalysts supported by common nitrogenated ligands can be used to tune a nitrene transfer reaction between two different types of C-H bonds. The results reported herein represent the first example of ligand-controlled and site-selective silver-promoted C-H amination.

  18. Synthesis of propargylic and allenic carbamates via the C-H amination of alkynes. (United States)

    Grigg, R David; Rigoli, Jared W; Pearce, Simon D; Schomaker, Jennifer M


    Propargylic amines are important intermediates for the synthesis of nitrogen-containing heterocycles. The insertion of a nitrene into a propargylic C-H bond has not been explored, despite the attention directed toward the Rh-catalyzed amination of other types of C-H bonds. In this communication, the conversion of a series of homopropargylic carbamates to propargylic carbamates and aminated allenes is described. © 2011 American Chemical Society

  19. Visible light-driven C-H activation and C-C coupling of methanol into ethylene glycol. (United States)

    Xie, Shunji; Shen, Zebin; Deng, Jiao; Guo, Pu; Zhang, Qinghong; Zhang, Haikun; Ma, Chao; Jiang, Zheng; Cheng, Jun; Deng, Dehui; Wang, Ye


    The development of new methods for the direct transformation of methanol into two or multi-carbon compounds via controlled carbon-carbon coupling is a highly attractive but challenging goal. Here, we report the first visible-light-driven dehydrogenative coupling of methanol into ethylene glycol, an important chemical currently produced from petroleum. Ethylene glycol is formed with 90% selectivity and high efficiency, together with hydrogen over a molybdenum disulfide nanofoam-modified cadmium sulfide nanorod catalyst. Mechanistic studies reveal a preferential activation of C-H bond instead of O-H bond in methanol by photoexcited holes on CdS via a concerted proton-electron transfer mechanism, forming a hydroxymethyl radical (⋅CH 2 OH) that can readily desorb from catalyst surfaces for subsequent coupling. This work not only offers an alternative nonpetroleum route for the synthesis of EG but also presents a unique visible-light-driven catalytic C-H activation with the hydroxyl group in the same molecule keeping intact.

  20. Catalytic diastereoselective tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts by C-C bond cleavage

    KAUST Repository

    Yang, Wenguo


    Through the cleavage of the C-C bond, the first catalytic tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts has been presented. Various S N2′-like C-, S-, and P-allylic compounds could be obtained with exclusive E configuration in good to excellent yields. The Michael product could also be easily prepared by tuning the β-C-substituent group of the α-methylene ester under the same reaction conditions. Calculated relative energies of various transition states by DFT methods strongly support the observed chemoselectivity and diastereoselectivity. © 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

  1. C-C Double Bond Cleavage of Linear α,β-Unsaturated Ketones

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Sung Gon; Jun, Chul Ho [Yonsei University, Seoul (Korea, Republic of)


    In conclusion, we have demonstrated the C-C double bond cleavage of α,β-unsaturated ketone under a catalytic system consisting of Rh(I) complex, 2-amino-3-picoline, cyclohexylamine, and benzoic acid. This reaction undergoes a retro-Mannich-type fragmentation of α,β-unsaturated ketone through the conjugate addition of cyclohexylamine followed by Rh(I)-catalyzed C-H bond activation. The activation of C-H bonds by transition-metal complexes is one of the most efficient methods to form C-C bonds in organic synthesis. We have successfully developed a Rh(I)-catalyzed C-H bond activation series using 2-amino-pyridine derivatives or benzylamine as a chelation auxiliary to induce cyclometalation. In the course of our studies on chelation-assisted C-H bond activation, we reported a Rh(I)-catalyzed hydroiminoacylation of alkynes with allylamine derivatives or aldehydes, which was further applied to the retro-Mannich-type fragmentation of the resulting α,β-unsaturated ketimine by primary amines. Encouraged by these results, we also developed a Rh(I)-catalyzed C-H bond activation of the ring opening in 2-cycloalkenones and a chelation-assisted β-alkylation of α,β-unsaturated ketone using Rh(I) catalyst and various amines.

  2. C-C Double Bond Cleavage of Linear α,β-Unsaturated Ketones

    International Nuclear Information System (INIS)

    Lim, Sung Gon; Jun, Chul Ho


    In conclusion, we have demonstrated the C-C double bond cleavage of α,β-unsaturated ketone under a catalytic system consisting of Rh(I) complex, 2-amino-3-picoline, cyclohexylamine, and benzoic acid. This reaction undergoes a retro-Mannich-type fragmentation of α,β-unsaturated ketone through the conjugate addition of cyclohexylamine followed by Rh(I)-catalyzed C-H bond activation. The activation of C-H bonds by transition-metal complexes is one of the most efficient methods to form C-C bonds in organic synthesis. We have successfully developed a Rh(I)-catalyzed C-H bond activation series using 2-amino-pyridine derivatives or benzylamine as a chelation auxiliary to induce cyclometalation. In the course of our studies on chelation-assisted C-H bond activation, we reported a Rh(I)-catalyzed hydroiminoacylation of alkynes with allylamine derivatives or aldehydes, which was further applied to the retro-Mannich-type fragmentation of the resulting α,β-unsaturated ketimine by primary amines. Encouraged by these results, we also developed a Rh(I)-catalyzed C-H bond activation of the ring opening in 2-cycloalkenones and a chelation-assisted β-alkylation of α,β-unsaturated ketone using Rh(I) catalyst and various amines

  3. Cobalt-Catalyzed Tandem C-H Activation/C-C Cleavage/C-H Cyclization of Aromatic Amides with Alkylidenecyclopropanes. (United States)

    Li, Mingliang; Kwong, Fuk Yee


    A cobalt-catalyzed chelation-assisted tandem C-H activation/C-C cleavage/C-H cyclization of aromatic amides with alkylidenecyclopropanes (ACPs) is reported. This process allows the sequential formation of two C-C bonds, in which it is in sharp contrast to previous report of using Rh catalyst for the formation of C-N bond. Here the inexpensive catalyst system exhibits good functional group compatibility and relatively broad substrate scope. The desired products can be easily transformed into polycyclic lactones with m-CPBA. Mechanistic studies revealed that the tandem reaction proceeds through a sequential C-H cobaltation, β-carbon elimination and intramolecular C-H cobaltation pathway. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Diffusion and Bonding Mechanism of Protective γ-Al2O3 on FeCrAl Foil for Metallic Three-Way Catalytic Converter

    Directory of Open Access Journals (Sweden)

    Feriyanto Dafit


    Full Text Available High pollutant level contributed by mobile sources/land transportation that become main problems for the human health. Improving exhaust emission system by improving catalytic converter properties is one of the most effective way to produce healthy air in our environment. It is conducted by two methods i.e. ultrasonic during electroplating (UBDEL and electroplating process (EL which are not fully investigated yet as catalytic converter coating process. UBDEL is conducted using sulphamate types electrolyte solution, Frequency of 35 kHz, current of 1.28A, Voltage of 12 V, and various time of 15, 30, 45, 60 and 75 minutes. Meanwhile El method is conducted using parameters of current of 1.28A, Voltage of 12 V, stirrer speed of 60 rpm and various time of 15, 30, 45, 60 and 75 minutes. Fully γ-Al2O3 bonding to the FeCrAl substrate is shown by UBDEL 75 minutes samples proved by SEM images and Ra and Rq are 4.01 μm and 5.64 μm, respectively. Ni present on the FeCrAl substrate as other protective layer generated by Ni electroplating process that will improve thermal stability of FeCrAl at high temperature of 1000 °C. From the results, can summarized that UBDEL technique is promoted as an effective catalytic converter coating technique.

  5. Metal-ligand cooperation by aromatization-dearomatization as a tool in single bond activation. (United States)

    Milstein, David


    Metal-ligand cooperation (MLC) plays an important role in bond activation processes, enabling many chemical and biological catalytic reactions. A recent new mode of activation of chemical bonds involves ligand aromatization-dearomatization processes in pyridine-based pincer complexes in which chemical bonds are broken reversibly across the metal centre and the pincer-ligand arm, leading to new bond-making and -breaking processes, and new catalysis. In this short review, such processes are briefly exemplified in the activation of C-H, H-H, O-H, N-H and B-H bonds, and mechanistic insight is provided. This new bond activation mode has led to the development of various catalytic reactions, mainly based on alcohols and amines, and to a stepwise approach to thermal H2 and light-induced O2 liberation from water. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

  6. Molecular Dynamics of Dimethyldioxirane C-H Oxidation. (United States)

    Yang, Zhongyue; Yu, Peiyuan; Houk, K N


    We report molecular dynamics simulations of the reaction of dimethyldioxirane (DMDO) with isobutane. The reaction involves hydrogen atom abstraction in the transition state, and trajectories branch to the oxygen rebound pathway, which gives tert-butanol and acetone, or a separated radical pair. In the gas phase, only 10% of the reactive trajectories undergo the oxygen rebound pathway, but this increases to 90% in simulations in an implicit acetone solvent (SMD) because the oxygen rebound becomes barrierless in solution. Short-lived diradical species were observed in the oxygen rebound trajectories. The time gap between C-H bond-breaking and C-O bond formation ranges from 30 to 150 fs, close to the <200 fs lifetime of radical pairs from DMDO hydroxylation of trans-1-phenyl-2-ethylcyclopropane measured by Newcomb.

  7. Sulfonamides as new hydrogen atom transfer (HAT) catalysts for photoredox allylic and benzylic C-H arylations. (United States)

    Tanaka, Hirotaka; Sakai, Kentaro; Kawamura, Atsushi; Oisaki, Kounosuke; Kanai, Motomu


    A catalytic amount of a sterically and electronically tuned diarylsulfonamide promoted allylic and benzylic C-H arylations in cooperation with a visible light photoredox catalyst. This is the first example of the catalytic use of a sulfonamidyl radical to promote the hydrogen atom transfer process.

  8. Decorative a-C:H coatings

    Czech Academy of Sciences Publication Activity Database

    Černý, F.; Jech, V.; Štěpánek, I.; Macková, Anna; Konvičková, S.

    roč. 256, 3 s. 1 (2009), s77-s81 ISSN 0169-4332 Institutional research plan: CEZ:AV0Z10480505 Keywords : a-C:H films * decorative coatings * adhesion Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.616, year: 2009

  9. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter


    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...

  10. Combined enzyme and substrate design: grafting of a cooperative two-histidine catalytic motif into a protein targeted at the scissile bond in a designed ester substrate. (United States)

    Höst, Gunnar E; Razkin, Jesus; Baltzer, Lars; Jonsson, Bengt-Harald


    A histidine-based, two-residue reactive site for the catalysis of hydrolysis of designed sulfonamide-containing para-nitrophenyl esters has been engineered into a scaffold protein. A matching substrate was designed to exploit the natural active site of human carbonic anhydrase II (HCAII) for well-defined binding. In this we took advantage of the high affinity between the active site zinc atom and sulfonamides. The ester substrate was designed to position the scissile bond in close proximity to the His64 residue in the scaffold protein. Three potential sites for grafting the catalytic His-His pair were identified, and the corresponding N62H/H64, F131H/V135H and L198H/P202H mutants were constructed. The most efficient variant, F131H/V135H, has a maximum k(cat)/K(M) value of approximately 14 000 M(-1) s(-1), with a k(cat) value that is increased by a factor of 3 relative to that of the wild-type HCAII, and by a factor of over 13 relative to the H64A mutant. The results show that an esterase can be designed in a stepwise way by a combination of substrate design and grafting of a designed catalytic motif into a well-defined substrate binding site.

  11. Removal of distal protein-water hydrogen bonds in a plant epoxide hydrolase increases catalytic turnover but decreases thermostability


    Thomaeus, Ann; Naworyta, Agata; Mowbray, Sherry L.; Widersten, Mikael


    A putative proton wire in potato soluble epoxide hydrolase 1, StEH1, was identified and investigated by means of site-directed mutagenesis, steady-state kinetic measurements, temperature inactivation studies, and X-ray crystallography. The chain of hydrogen bonds includes five water molecules coordinated through backbone carbonyl oxygens of Pro186, Leu266, His269, and the His153 imidazole. The hydroxyl of Tyr149 is also an integrated component of the chain, which leads to the hydroxyl of Tyr1...

  12. 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.

  13. Regioselective oxidative trifluoromethylation of imidazoheterocycles via C(sp2)-H bond functionalization. (United States)

    Monir, Kamarul; Bagdi, Avik Kumar; Ghosh, Monoranjan; Hajra, Alakananda


    Catalytic oxidative trifluoromethylation of imidazopyridines has been carried out at room temperature through the functionalization of the sp(2) C-H bond employing Langlois reagent under ambient air. A library of 3-(trifluoromethyl)imidazo[1,2-a]pyridines with broad functionalities have been synthesized regioselectively. This methodology is also applicable to imidazo[2,1-b]thiazole and benzo[d]imidazo[2,1-b]thiazole.

  14. Selective catalytic hydrogenation of the N-acyl and uridyl double bonds in the tunicamycin family of protein N-glycosylation inhibitors. (United States)

    Price, Neil Pj; Jackson, Michael A; Vermillion, Karl E; Blackburn, Judith A; Li, Jiakun; Yu, Biao


    Tunicamycin is a Streptomyces-derived inhibitor of eukaryotic protein N-glycosylation and bacterial cell wall biosynthesis, and is a potent and general toxin by these biological mechanisms. The antibacterial activity is dependent in part upon a π-π stacking interaction between the tunicamycin uridyl group and a specific Phe residue within MraY, a tunicamycin-binding protein in bacteria. We have previously shown that reducing the tunicamycin uridyl group to 5,6-dihydrouridyl (DHU) significantly lowers its eukaryotic toxicity, potentially by disrupting the π-stacking with the active site Phe. The present report compares the catalytic hydrogenation of tunicamycin and uridine with various precious metal catalysts, and describe optimum conditions for the selective production of N-acyl reduced tunicamycin or for tunicamycins reduced in both the N-acyl and uridyl double bonds. At room temperature, Pd-based catalysts are selective for the N-acyl reduction, whereas Rh-based catalysts favor the double reduction to provide access to fully reduced tunicamycin. The reduced DHU is highly base-sensitive, leading to amide ring opening under mild alkaline conditions.

  15. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes. (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata


    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  16. Ru(II)-catalyzed intermolecular ortho-C-H amidation of aromatic ketones with sulfonyl azides. (United States)

    Bhanuchandra, M; Yadav, M Ramu; Rit, Raja K; Rao Kuram, Malleswara; Sahoo, Akhila K


    Ru(II)-catalyzed intermolecular ortho-C-H amidation of weakly coordinating aromatic ketones with sulfonyl azides is reported. The developed reaction protocol can be extended to various substituted aromatic ketones to afford a wide range of desired C-N bond formation products in good yields.

  17. References (Examples) Journals Desiraju G R 1991 The C-H...O ...

    Indian Academy of Sciences (India)


    References (Examples). Journals. Desiraju G R 1991 The C-H...O Hydrogen Bond in Crystals: What is it? Acc. Chem. Res. 24 290. Beer P D and Gale P A 2001 Anion Recognition and Sensing: The State of the Art and Future. Perspectives Angew. Chem. Int. Edit. 40 486. Chakraborty A, Kar S, Nath D N and Guchhait N ...

  18. Catalytic Oligopeptide Synthesis. (United States)

    Liu, Zijian; Noda, Hidetoshi; Shibasaki, Masakatsu; Kumagai, Naoya


    Waste-free catalytic assembly of α-amino acids is fueled by a multiboron catalyst that features a characteristic B 3 NO 2 heterocycle, providing a versatile catalytic protocol wherein functionalized natural α-amino acid units are accommodated and commonly used protecting groups are tolerated. The facile dehydrative conditions eliminate the use of engineered peptide coupling reagents, exemplifying a greener catalytic alternative for peptide coupling. The catalysis is sufficiently robust to enable pentapeptide synthesis, constructing all four amide bond linkages in a catalytic fashion.

  19. Deposition and characterisation of multilayer hard coatings. Ti/TiNδ/TiCxNy/(TiC) a-C:H/(Ti) a-C:H

    International Nuclear Information System (INIS)

    Burinprakhon, T.


    Multilayer hard coatings containing Ti, TiNδ, TiC x N y , (TiC m ) a-C:H, (TiC 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 2 , Ar+N 2 +CH 4 , and Ar+CH 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 TiNδ and TiC x N y interlayers, the a-C:H interlayers containing graded titanium and nitrogen contents were found to develop successively to the TiC x N y interlayer without the formation of near-stoichiometric TiC. The (TiC m ) a-C:H interlayer consisted of nano-particles of distorted fcc crystal structure embedded in the a-C:H matrix. The (TiC 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 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 2 contamination during deposition caused by low conductance of N 2 through the nominally closed valve of the mass flow controller. The change of the CH 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 4 concentration of less than 50 % flow rate in Ar. The hardness

  20. Catalytic reforming methods (United States)

    Tadd, Andrew R; Schwank, Johannes


    A catalytic reforming method is disclosed herein. The method includes sequentially supplying a plurality of feedstocks of variable compositions to a reformer. The method further includes adding a respective predetermined co-reactant to each of the plurality of feedstocks to obtain a substantially constant output from the reformer for the plurality of feedstocks. The respective predetermined co-reactant is based on a C/H/O atomic composition for a respective one of the plurality of feedstocks and a predetermined C/H/O atomic composition for the substantially constant output.

  1. Alcohols as alkylating agents in heteroarene C-H functionalization (United States)

    Jin, Jian; MacMillan, David W. C.


    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of `spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  2. Catalytic conversion of methane to methanol using Cu-zeolites. (United States)

    Alayon, Evalyn Mae C; Nachtegaal, Maarten; Ranocchiari, Marco; van Bokhoven, Jeroen A


    The conversion of methane to value-added liquid chemicals is a promising answer to the imminent demand for fuels and chemical synthesis materials in the advent of a dwindling petroleum supply. Current technology requires high energy input for the synthesis gas production, and is characterized by low overall selectivity, which calls for alternative reaction routes. The limitation to achieve high selectivity is the high C-H bond strength of methane. High-temperature reaction systems favor gas-phase radical reactions and total oxidation. This suggests that the catalysts for methane activation should be active at low temperatures. The enzymatic-inspired metal-exchanged zeolite systems apparently fulfill this need, however, methanol yield is low and a catalytic process cannot yet be established. Homogeneous and heterogeneous catalytic systems have been described which stabilize the intermediate formed after the first C-H activation. The understanding of the reaction mechanism and the determination of the active metal sites are important for formulating strategies for the upgrade of methane conversion catalytic technologies.

  3. Photoredox ketone catalysis for the direct C-H imidation and acyloxylation of arenes. (United States)

    Tripathi, Chandra Bhushan; Ohtani, Tsuyoshi; Corbett, Michael T; Ooi, Takashi


    The photoexcited aryl ketone-catalyzed C-H imidation of arenes and heteroarenes is reported. Using 3,6-dimethoxy-9 H -thioxanthen-9-one as a catalyst in combination with a bench-stable imidating reagent, C-N bond formation proceeds with high efficiency and a broad substrate scope. A key part of this method is that the thioxanthone catalyst acts as an excited-state reductant, thus establishing an oxidative quenching cycle for radical aromatic substitution. The synthetic potential of this photoexcited ketone catalysis is further demonstrated by application to the direct C-H acyloxylation of arenes.

  4. 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).

  5. Rh(iii)-catalyzed C-H olefination of N-pentafluoroaryl benzamides using air as the sole oxidant. (United States)

    Lu, Yi; Wang, Huai-Wei; Spangler, Jillian E; Chen, Kai; Cui, Pei-Pei; Zhao, Yue; Sun, Wei-Yin; Yu, Jin-Quan


    The oxidative olefination of a broad array of arenes and heteroarenes with a variety of activated and unactivated olefins has be achieved via a rhodium(iii)-catalyzed C-H activation reaction. The use of an N -pentafluorophenyl benzamide directing group is crucial for achieving catalytic turnovers in the presence of air as the sole oxidant without using a co-oxidant.

  6. Cyanthiwigin Natural Product Core as a Complex Molecular Scaffold for Comparative Late-Stage C-H Functionalization Studies. (United States)

    Kim, Kelly E; Adams, Ashley M; Chiappini, Nicholas D; Du Bois, J; Stoltz, Brian M


    The desire for maximally efficient transformations in complex molecule synthesis has contributed to a surge of interest in C-H functionalization methods development in recent years. In contrast to the steady stream of methodological reports, however, there are noticeably fewer studies comparing the efficacies of different C-H functionalization protocols on a single structurally intricate substrate. Recognizing the importance of heteroatom incorporation in complex molecule synthesis, this report discloses a comparative examination of diverse strategies for C-O, C-N, and C-X bond formation through late-stage C-H oxidation of the tricyclic cyanthiwigin natural product core. Methods for allylic C-H acetoxylation, tertiary C-H hydroxylation, tertiary C-H amination, tertiary C-H azidation, and secondary C-H halogenation are explored. These efforts highlight the robustness and selectivities of many well-established protocols for C-H oxidation when applied to a complex molecular framework, and the findings are relevant to chemists aiming to employ such strategies in the context of chemical synthesis.

  7. Elaboration of copper-oxygen mediated C-H activation chemistry in consideration of future fuel and feedstock generation. (United States)

    Lee, Jung Yoon; Karlin, Kenneth D


    To contribute solutions to current energy concerns, improvements in the efficiency of dioxygen mediated C-H bond cleavage chemistry, for example, selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, potentially affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Spectroscopic Study of Plasma Polymerized a-C:H Films Deposited by a Dielectric Barrier Discharge. (United States)

    Chandrashekaraiah, Thejaswini Halethimmanahally; Bogdanowicz, Robert; Rühl, Eckart; Danilov, Vladimir; Meichsner, Jürgen; Thierbach, Steffen; Hippler, Rainer


    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 C₂H m /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 sp ³ and sp ² 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 I D /I G 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.

  9. Oxidant-free Rh(III)-catalyzed direct C-H olefination of arenes with allyl acetates. (United States)

    Feng, Chao; Feng, Daming; Loh, Teck-Peng


    Rh(III)-catalyzed direct olefination of arenes with allyl acetate via C-H bond activation is described using N,N-disubstituted aminocarbonyl as the directing group. The catalyst undergoes a redox neutral process, and high to excellent yields of trans-products are obtained. This protocol exhibits a wide spectrum of functionality compatibility because of the simple reaction conditions employed and provides a highly effective synthetic method in the realm of C-H olefination.

  10. Iridium complexes containing mesoionic C donors: selective C(sp3)-H versus C(sp2)-H bond activation, reactivity towards acids and bases, and catalytic oxidation of silanes and water. (United States)

    Petronilho, Ana; Woods, James A; Mueller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin


    Metalation of a C2-methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp(3))-H bond activation of the C2-bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp(2))-H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp(2))-H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D(+) and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir-C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6,000 h(-1) with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol-4-ylidene ligands and is more than three times faster than with the triazolylidene analogue. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. C-H activation on rhodium: reaction mechanism and the role of carbonaceous residues

    International Nuclear Information System (INIS)

    Cogen, J.M.; Maier, W.F.


    Evidence for two C-H activation mechanisms, the oxidative addition of a single C-H bond and the concerted oxidative addition of two adjacent C-H bonds, is presented. The two mechanisms show different sensitivity to surface structure or particle size. While the first process (E/sub a/ ∼ 21 kcal/mol) is insensitive to the hydrocarbon structure, the second process (E/sub a/ ∼ 5-9 kcal/mol) is sensitive to the hydrocarbon structure. C-H activation is found to be 0.6 order in hexane and zero order in deuterium, which is consistent with oxidative addition as the rate-determining step. The d 2 maximum obtained by H/D exchange of linear alkanes on Rh results from surface olefins, as indicated by high-resolution deuterium NMR. Evidence against the participation of carbonaceous residues in the H/D exchange process is presented, indicating that carbonaceous material is not part of the active site. Two types of carbonaceous residues are detected. One forms at lower temperatures and does not interfere with the reaction; the other forms at higher temperatures and acts to poison the catalyst

  12. Ligand-accelerated non-directed C-H functionalization of arenes (United States)

    Wang, Peng; Verma, Pritha; Xia, Guoqin; Shi, Jun; Qiao, Jennifer X.; Tao, Shiwei; Cheng, Peter T. W.; Poss, Michael A.; Farmer, Marcus E.; Yeung, Kap-Sun; Yu, Jin-Quan


    The directed activation of carbon-hydrogen bonds (C-H) is important in the development of synthetically useful reactions, owing to the proximity-induced reactivity and selectivity that is enabled by coordinating functional groups. Palladium-catalysed non-directed C-H activation could potentially enable further useful reactions, because it can reach more distant sites and be applied to substrates that do not contain appropriate directing groups; however, its development has faced substantial challenges associated with the lack of sufficiently active palladium catalysts. Currently used palladium catalysts are reactive only with electron-rich arenes, unless an excess of arene is used, which limits synthetic applications. Here we report a 2-pyridone ligand that binds to palladium and accelerates non-directed C-H functionalization with arene as the limiting reagent. This protocol is compatible with a broad range of aromatic substrates and we demonstrate direct functionalization of advanced synthetic intermediates, drug molecules and natural products that cannot be used in excessive quantities. We also developed C-H olefination and carboxylation protocols, demonstrating the applicability of our methodology to other transformations. The site selectivity in these transformations is governed by a combination of steric and electronic effects, with the pyridone ligand enhancing the influence of sterics on the selectivity, thus providing complementary selectivity to directed C-H functionalization.

  13. 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.

  14. Pd-Catalyzed regioselective C-H halogenation of quinazolinones and benzoxazinones. (United States)

    Dabiri, Minoo; Farajinia Lehi, Noushin; Kazemi Movahed, Siyavash; Khavasi, Hamid Reza


    A Pd-catalyzed ortho-selective halogenation of benzoxazinone and quinazolinone scaffolds has been described employing N-halosuccinimide as both a halogen source and an oxidant reagent via C-H bond activation. This transformation shows high chemo- and regioselectivities and demonstrates a broad range of benzoxazinone and quinazolinone substrates with different functional groups and has been scaled up to the gram level.

  15. Palladium(II)-catalyzed ortho-C-H arylation/alkylation of N-benzoyl α-amino ester derivatives. (United States)

    Misal Castro, Luis C; Chatani, Naoto


    The palladium-catalyzed arylation/alkylation of ortho-C-H bonds in N-benzoyl α-amino ester derivatives is described. In such a system both the NH-amido and the CO2R groups in the α-amino ester moieties play a role in successful C-H activation/C-C bond formation using iodoaryl coupling partners. A wide variety of functional groups and electron-rich/deficient iodoarenes are tolerated. The yields obtained range from 20 to 95%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Electrooxidative Rhodium-Catalyzed C-H/C-H Activation: Electricity as Oxidant for Cross-Dehydrogenative Alkenylation. (United States)

    Qiu, Youai; Kong, Wei-Jun; Struwe, Julia; Sauermann, Nicolas; Rogge, Torben; Scheremetjew, Alexej; Ackermann, Lutz


    Rhodium(III) catalysis has enabled a plethora of oxidative C-H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we describe the first electrochemical C-H activation by rhodium catalysis that avoids hazardous chemical oxidants. Thus, environmentally-benign twofold C-H/C-H functionalizations were accomplished with weakly-coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant with H2 as the sole byproduct. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Ir-catalyzed C-H silylations of phenyldeazapurines

    Czech Academy of Sciences Publication Activity Database

    Sabat, Nazarii; Poštová Slavětínská, Lenka; Hocek, Michal


    Roč. 56, č. 49 (2015), s. 6860-6862 ISSN 0040-4039 Institutional support: RVO:61388963 Keywords : C-H silylation * deazapurines * iridium catalysis * C-H activations Subject RIV: CC - Organic Chemistry Impact factor: 2.347, year: 2015

  18. Sequential meta-C-H olefination of synthetically versatile benzyl silanes: effective synthesis of meta-olefinated toluene, benzaldehyde and benzyl alcohols. (United States)

    Patra, Tuhin; Watile, Rahul; Agasti, Soumitra; Naveen, Togati; Maiti, Debabrata


    Tremendous progress has been made towards ortho-selective C-H functionalization in the last three decades. However, the activation of distal C-H bonds and their functionalization has remained fairly underdeveloped. Herein, we report sequential meta-C-H functionalization by performing selective mono-olefination and bis-olefination with late stage modification of the C-Si as well as Si-O bonds. Temporary silyl connection was found to be advantageous due to its easy installation, easy removal and wide synthetic diversification.

  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. Photochemical studies of (η5-C5H5)Ru(PPh3)2Cl and (η5-C5H5)Ru(PPh3)2Me: formation of Si-H and C-H bond activation products. (United States)

    Clark, Johnathan L; Duckett, Simon B


    Studies examining the photochemical reactivity of CpRu(PPh3)2Cl and CpRu(PPh3)2Me towards the two electron donor ligands PEt3, C2H4, DMSO, the CH bond activatable reagents tetrahydrofuran, toluene, and pyridine, and the SiH bond activatable reagents HSiEt3 and HSi(Me)2CH=CH2) are presented. Broadband UV irradiation of CpRu(PPh3)2Cl leads to the formation of mono-substitution products such as CpRu(PPh3)(PEt3)Cl which are inert to further photochemical reaction, although thermally bis-substituted products such as CpRu(PEt3)2Cl can be formed. Room temperature irradiation of the related complex CpRu(PPh3)2Me with L = PEt3, C2H4, and DMSO also produces CpRu(PPh3)(L)Me. However, when these reactions are followed by in situ laser irradiation (325 nm source) at low temperature, three solvent activated isomers (ortho, meta and para) of CpRu(PPh3)2(C6H4Me) are detected in toluene in addition to η(1)- and η(3)-coordinated benzyl species. Furthermore, photolysis in THF leads to both the C-D bond activation product CpRu(PPh3)2(OC4D7) and the labile coordination complex CpRu(PPh3)(THF)Me. Now CH4 rather than CH3D is liberated which suggests the involvement of an orthometallated species. The photochemically driven reaction of CpRu(PPh3)2Me with HSiEt3 at 198 K generates CpRu(κ(2)-2-C6H4PPh2)(SiEt3)H and thereby confirms a role for an orthometallated complex is this process. Irradiation in cyclohexane produces the known orthometallated complex, CpRu(κ(2)-2-C6H4PPh2)(PPh3), and CH4 in accordance with this reactivity.

  1. Ru(II)-catalyzed selective C-H amination of xanthones and chromones with sulfonyl azides: synthesis and anticancer evaluation. (United States)

    Shin, Youngmi; Han, Sangil; De, Umasankar; Park, Jihye; Sharma, Satyasheel; Mishra, Neeraj Kumar; Lee, Eui-Kyung; Lee, Youngil; Kim, Hyung Sik; Kim, In Su


    A ketone-assisted ruthenium-catalyzed selective amination of xanthones and chromones C-H bonds with sulfonyl azides is described. The reactions proceed efficiently with a broad range of substrates with excellent functional group compatibility. This protocol provides direct access to 1-aminoxanthones, 5-aminochromones, and 5-aminoflavonoid derivatives known to exhibit potent anticancer activity.

  2. Measurement of the C / H ratio using neutrons

    International Nuclear Information System (INIS)

    Martinelli, P.


    A probe made up of a Ra (α, n) Be neutron source and a proportional counter filled with boron trifluoride has been used to measure the C/H ratio in hydrocarbons. The intensity of the thermal neutron flux in the neighbourhood of the detector increases with the concentration of the hydrocarbon hydrogen surrounding it. By measuring the density it is possible to deduce the C/H ratio. It is thus possible to evaluate the C/H ratio with a precision equal to that given by the β-ray transmission method. The errors arising from the chemical nature of the hydrocarbon can be reduced to a minimum. This method has the advantage of allowing the measurement of the C/H ratio of hydrocarbons contained in recipients or thick steel tubing by means an independent portable apparatus. (author) [fr

  3. 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.

  4. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter


    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...... for the development of allylic C-H alkylation into a widely applicable methodology, thus providing a means to enhance synthetic efficiency in these reactions....

  5. General allylic C-H alkylation with tertiary nucleophiles. (United States)

    Howell, Jennifer M; Liu, Wei; Young, Andrew J; White, M Christina


    A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.

  6. 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.

  7. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation (United States)

    Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.


    The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C-H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C-H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

  8. The C-terminal domain of human grp94 protects the catalytic subunit of protein kinase CK2 (CK2alpha) against thermal aggregation. Role of disulfide bonds

    DEFF Research Database (Denmark)

    Roher, N; Miró, F; Boldyreff, B


    The C-terminal domain (residues 518-803) of the 94 kDa glucose regulated protein (grp94) was expressed in Escherichia coli as a fusion protein with a His6-N-terminal tag (grp94-CT). This truncated form of grp94 formed dimers and oligomers that could be dissociated into monomers by treatment...... with dithiothreitol. Grp94-CT conferred protection against aggregation on the catalytic subunit of protein kinase CK2 (CK2alpha), although it did not protect against thermal inactivation. This anti-aggregation effect of grp94-CT was concentration dependent, with full protection achieved at grp94-CT/CK2alpha molar...

  9. 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.

  10. A broken-symmetry density functional study of structures, energies, and protonation states along the catalytic O-O bond cleavage pathway in ba3 cytochrome c oxidase from Thermus thermophilus. (United States)

    Han Du, Wen-Ge; Götz, Andreas W; Yang, Longhua; Walker, Ross C; Noodleman, Louis


    Broken-symmetry density functional calculations have been performed on the [Fea3, CuB] dinuclear center (DNC) of ba3 cytochrome c oxidase from Thermus thermophilus in the states of [Fea3(3+)-(HO2)(-)-CuB(2+), Tyr237(-)] and [Fea3(4+)[double bond, length as m-dash]O(2-), OH(-)-CuB(2+), Tyr237˙], using both PW91-D3 and OLYP-D3 functionals. Tyr237 is a special tyrosine cross-linked to His233, a ligand of CuB. The calculations have shown that the DNC in these states strongly favors the protonation of His376, which is above propionate-A, but not of the carboxylate group of propionate-A. The energies of the structures obtained by constrained geometry optimizations along the O-O bond cleavage pathway between [Fea3(3+)-(O-OH)(-)-CuB(2+), Tyr237(-)] and [Fea3(4+)[double bond, length as m-dash]O(2-)HO(-)-CuB(2+), Tyr237˙] have also been calculated. The transition of [Fea3(3+)-(O-OH)(-)-CuB(2+), Tyr237(-)] → [Fea3(4+)[double bond, length as m-dash]O(2-)HO(-)-CuB(2+), Tyr237˙] shows a very small barrier, which is less than 3.0/2.0 kcal mol(-1) in PW91-D3/OLYP-D3 calculations. The protonation state of His376 does not affect this O-O cleavage barrier. The rate limiting step of the transition from state A (in which O2 binds to Fea3(2+)) to state PM ([Fea3(4+)[double bond, length as m-dash]O(2-), OH(-)-CuB(2+), Tyr237˙], where the O-O bond is cleaved) in the catalytic cycle is, therefore, the proton transfer originating from Tyr237 to O-O to form the hydroperoxo [Fea3(3+)-(O-OH)(-)-CuB(2+), Tyr237(-)] state. The importance of His376 in proton uptake and the function of propionate-A/neutral-Asp372 as a gate to prevent the proton from back-flowing to the DNC are also shown.

  11. Rhodium-catalyzed enantioselective intramolecular C-H silylation for the syntheses of planar-chiral metallocene siloles. (United States)

    Zhang, Qing-Wei; An, Kun; Liu, Li-Chuan; Yue, Yuan; He, Wei


    Reported herein is the rhodium-catalyzed enantioselective C-H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)-TMS-Segphos, the reactions took place under very mild conditions to afford metallocene-fused siloles in good to excellent yields and with ee values of up to 97%. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C-H silylations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Atomic and electronic structures of a-SiC:H from tight-binding molecular dynamics

    CERN Document Server

    Ivashchenko, V I; Shevchenko, V I; Ivashchenko, L A; Rusakov, G V


    The atomic and electronic properties of amorphous unhydrogenated (a-SiC) and hydrogenated (a-SiC:H) silicon carbides are studied using an sp sup 3 s sup * tight-binding force model with molecular dynamics simulations. The parameters of a repulsive pairwise potential are determined from ab initio pseudopotential calculations. Both carbides are generated from dilute vapours condensed from high temperature, with post-annealing at low temperature for a-SiC:H. A plausible model for the inter-atomic correlations and electronic states in a-SiC:H is suggested. According to this model, the formation of the amorphous network is weakly sensitive to the presence of hydrogen. Hydrogen passivates effectively only the weak bonds of threefold-coordinated atoms. Chemical ordering is very much affected by the cooling rate and the structure of the high-temperature vapour. The as-computed characteristics are in rather good agreement with the results for a-SiC and a-Si:H from ab initio calculations.

  13. Properties of a-C:H:O plasma polymer films deposited from acetone vapors

    Energy Technology Data Exchange (ETDEWEB)

    Drabik, M., E-mail: [Empa, Swiss Federal Laboratories for Materials Science and Technology, Lerchenfeldstrasse 5, 9014 St. Gallen (Switzerland); Celma, C. [Empa, Swiss Federal Laboratories for Materials Science and Technology, Lerchenfeldstrasse 5, 9014 St. Gallen (Switzerland); Kousal, J.; Biederman, H. [Charles University in Prague, Faculty of Mathematics and Physics, Department of Macromolecular Physics, V Holešovičkách 2, 180 00 Prague 8 (Czech Republic); Hegemann, D. [Empa, Swiss Federal Laboratories for Materials Science and Technology, Lerchenfeldstrasse 5, 9014 St. Gallen (Switzerland)


    To gain insight into the deposition and stability of oxygen-containing plasma polymer films, the properties of amorphous oxygenated hydrocarbon (a-C:H:O) plasma polymer coatings deposited from acetone vapors under various experimental conditions are investigated. Apart from the discharge power, the influence of the reactive carbon dioxide (CO{sub 2}) gas on the structure of the resulting films is studied. It is found by characterization using X-ray Photoelectron Spectroscopy and Fourier-Transform Infrared Spectroscopy that the experimental conditions particularly influence the amount of oxygen in the deposited a-C:H:O plasma polymer films. The O/C elemental ratio increases with increasing amount of CO{sub 2} in the working gas mixture (up to 0.2 for 24 sccm of CO{sub 2} at 30 W) and decreases with increasing RF discharge power (down to 0.17 for 50 W). Furthermore, the nature of bonds between the oxygen and carbon atoms has been examined. Only low amounts of double and triple bonded carbon are observed. This has a particular influence on the aging of the plasma polymer films which is studied both in ambient air and in distilled water for up to 4 months. Overall, stable a-C:H:O plasma polymer films are deposited comprising low amounts (up to about 5%) of ester/carboxyl groups. - Highlights: • Hydrocarbon plasma polymer films with variable oxygen content can be prepared. • Stable oxygenated hydrocarbon plasma polymers contain max 5% of ester/carboxyl groups. • Acetone-derived plasma polymer films can be used as permanent hydrophilic surfaces.

  14. Exploration of earth-abundant transition metals (Fe, Co, and Ni) as catalysts in unreactive chemical bond activations. (United States)

    Su, Bo; Cao, Zhi-Chao; Shi, Zhang-Jie


    Activation of inert chemical bonds, such as C-H, C-O, C-C, and so on, is a very important area, to which has been drawn much attention by chemists for a long time and which is viewed as one of the most ideal ways to produce valuable chemicals. Under modern chemical bond activation logic, many conventionally viewed "inert" chemical bonds that were intact under traditional conditions can be reconsidered as novel functionalities, which not only avoids the tedious synthetic procedures for prefunctionalizations and the emission of undesirable wastes but also inspires chemists to create novel synthetic strategies in completely different manners. Although activation of "inert" chemical bonds using stoichiometric amounts of transition metals has been reported in the past, much more attractive and challenging catalytic transformations began to blossom decades ago. Compared with the broad application of late and noble transition metals in this field, the earth-abundant first-row transition-metals, such as Fe, Co, and Ni, have become much more attractive, due to their obvious advantages, including high abundance on earth, low price, low or no toxicity, and unique catalytic characteristics. In this Account, we summarize our recent efforts toward Fe, Co, and Ni catalyzed "inert" chemical bond activation. Our research first unveiled the unique catalytic ability of iron catalysts in C-O bond activation of both carboxylates and benzyl alcohols in the presence of Grignard reagents. The benzylic C-H functionalization was also developed via Fe catalysis with different nucleophiles, including both electron-rich arenes and 1-aryl-vinyl acetates. Cobalt catalysts also showed their uniqueness in both aromatic C-H activation and C-O activation in the presence of Grignard reagents. We reported the first cobalt-catalyzed sp(2) C-H activation/arylation and alkylation of benzo[h]quinoline and phenylpyridine, in which a new catalytic pathway via an oxidative addition process was demonstrated

  15. Dual Ligand-Enabled Nondirected C-H Olefination of Arenes. (United States)

    Chen, Hao; Wedi, Philipp; Meyer, Tim; Tavakoli, Ghazal; van Gemmeren, Manuel


    The application of the Pd-catalyzed oxidative C-H olefination of arenes, also known as the Fujiwara-Moritani reaction, has traditionally been limited by the requirement for directing groups on the substrate or the need to use the arene in large excess, typically as a (co)solvent. Herein the development of a catalytic system is described that, through the combined action of two complementary ligands, makes it possible to use directing-group-free arenes as limiting reagents for the first time. The reactions proceed under a combination of both steric and electronic control and enable the application of this powerful reaction to valuable arenes, which cannot be utilized in excess. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Isomerization of Internal Alkynes to Iridium(III Allene Complexes via C–H Bond Activation: Expanded Substrate Scope, and Progress towards a Catalytic Methodology

    Directory of Open Access Journals (Sweden)

    Neha Phadke


    Full Text Available The synthesis of a series of allene complexes (POCOPIr(η2-RC=.=CR’ 1b–4b (POCOP = 2,6-bis(di-tert-butylphosphonitobenzene via isomerization of internal alkynes is reported. We have demonstrated that the application of this methodology is viable for the isomerization of a wide variety of alkyne substrates. Deuterium labeling experiments support our proposed mechanism. The structures of the allene complexes 1b–4b were determined using spectroscopic data analysis. Additionally, the solid-state molecular structure of complex 2b was determined using single crystal X-ray diffraction studies and it confirmed the assignment of an iridium-bound allene isomerization product. The rates of isomerization were measured using NMR techniques over a range of temperatures to allow determination of thermodynamic parameters. Finally, we report a preliminary step towards developing a catalytic methodology; the allene may be liberated from the metal center by exposure of the complex to an atmosphere of carbon monoxide.

  17. Oxyfunctionalization of the Remote C-H Bonds of Aliphatic Amines by Decatungstate Photocatalysis. (United States)

    Schultz, Danielle M; Lévesque, François; DiRocco, Daniel A; Reibarkh, Mikhail; Ji, Yining; Joyce, Leo A; Dropinski, James F; Sheng, Huaming; Sherry, Benjamin D; Davies, Ian W


    Aliphatic amines, oxygenated at remote positions within the molecule, represent an important class of synthetic building blocks to which there are currently no direct means of access. Reported herein is an efficient and scalable solution that relies upon decatungstate photocatalysis under acidic conditions using either H 2 O 2 or O 2 as the terminal oxidant. By using these reaction conditions a series of simple and unbiased aliphatic amine starting materials can be oxidized to value-added ketone products. Lastly, NMR spectroscopy using in situ LED-irradiated samples was utilized to monitor the kinetics of the reaction, thus enabling direct translation of the reaction into flow. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Activation of C-H bonds by rare-earth metallocene-butyl complexes. (United States)

    Grindell, Richard; Day, Benjamin M; Guo, Fu-Sheng; Pugh, Thomas; Layfield, Richard A


    The stable metallocene-butyl complexes [(Cp Me ) 2 M( n Bu)] 2 (M = Y, Dy) were synthesized and their reactivity towards to ferrocene and bulky N-heterocyclic carbenes investigated. Selective mono-deprotonation of ferrocene and a benzylic methyl group of IMes were observed, whereas a control reaction of (Cp Me ) 3 M with IMes resulted in a normal-to-abnormal NHC rearrangement.

  19. Crystal Structures of Two Bacterial 3-Hydroxy-3-methylglutaryl-CoA Lyases Suggest a Common Catalytic Mechanism among a Family of TIM Barrel Metalloenzymes Cleaving Carbon-Carbon Bonds

    Energy Technology Data Exchange (ETDEWEB)

    Forouhar,F.; Hussain, M.; Farid, R.; Benach, J.; Abashidze, M.; Edstrom, W.; Vorobiev, S.; Montelione, G.; Hunt, J.; et al.


    The enzyme 3-hydroxy-3-methylglutaryl-coenzyme A (HMG-CoA) lyase catalyzes the terminal steps in ketone body generation and leucine degradation. Mutations in this enzyme cause a human autosomal recessive disorder called primary metabolic aciduria, which typically kills victims because of an inability to tolerate hypoglycemia. Here we present crystal structures of the HMG-CoA lyases from Bacillus subtilis and Brucella melitensis at 2.7 and 2.3 {angstrom} resolution, respectively. These enzymes share greater than 45% sequence identity with the human orthologue. Although the enzyme has the anticipated triose-phosphate isomerase (TIM) barrel fold, the catalytic center contains a divalent cation-binding site formed by a cluster of invariant residues that cap the core of the barrel, contrary to the predictions of homology models. Surprisingly, the residues forming this cation-binding site and most of their interaction partners are shared with three other TIM barrel enzymes that catalyze diverse carbon-carbon bond cleavage reactions believed to proceed through enolate intermediates (4-hydroxy-2-ketovalerate aldolase, 2-isopropylmalate synthase, and transcarboxylase 5S). We propose the name 'DRE-TIM metallolyases' for this newly identified enzyme family likely to employ a common catalytic reaction mechanism involving an invariant Asp-Arg-Glu (DRE) triplet. The Asp ligates the divalent cation, while the Arg probably stabilizes charge accumulation in the enolate intermediate, and the Glu maintains the precise structural alignment of the Asp and Arg. We propose a detailed model for the catalytic reaction mechanism of HMG-CoA lyase based on the examination of previously reported product complexes of other DRE-TIM metallolyases and induced fit substrate docking studies conducted using the crystal structure of human HMG-CoA lyase (reported in the accompanying paper by Fu, et al. (2006) J. Biol. Chem. 281, 7526-7532). Our model is consistent with extensive mutagenesis

  20. Ruthenium(II) Complexes Containing Lutidine-Derived Pincer CNC Ligands: Synthesis, Structure, and Catalytic Hydrogenation of C-N bonds. (United States)

    Hernández-Juárez, Martín; López-Serrano, Joaquín; Lara, Patricia; Morales-Cerón, Judith P; Vaquero, Mónica; Álvarez, Eleuterio; Salazar, Verónica; Suárez, Andrés


    A series of Ru complexes containing lutidine-derived pincer CNC ligands have been prepared by transmetalation with the corresponding silver-carbene derivatives. Characterization of these derivatives shows both mer and fac coordination of the CNC ligands depending on the wingtips of the N-heterocyclic carbene fragments. In the presence of tBuOK, the Ru-CNC complexes are active in the hydrogenation of a series of imines. In addition, these complexes catalyze the reversible hydrogenation of phenantridine. Detailed NMR spectroscopic studies have shown the capability of the CNC ligand to be deprotonated and get involved in ligand-assisted activation of dihydrogen. More interestingly, upon deprotonation, the Ru-CNC complex 5 e(BF4 ) is able to add aldimines to the metal-ligand framework to yield an amido complex. Finally, investigation of the mechanism of the hydrogenation of imines has been carried out by means of DFT calculations. The calculated mechanism involves outer-sphere stepwise hydrogen transfer to the C-N bond assisted either by the pincer ligand or a second coordinated H2 molecule. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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.

  2. Insights into catalytic oxidation at the Au/TiO(2) dual perimeter sites. (United States)

    Green, Isabel X; Tang, Wenjie; Neurock, Matthew; Yates, John T


    Gold (Au) nanoparticles supported on reducible oxides such as TiO2 demonstrate exceptional catalytic activity for a wide range of gas phase oxidation reactions such as CO oxidation, olefin epoxidation, and water gas shift catalysis. Scientists have recently shifted their hypotheses on the origin of the reactivity of these materials from the unique electronic properties and under-coordinated Au sites on nanometer-sized particles to bifunctional sites at the Au-support interface. In this Account, we summarize our recent experimental and theoretical results to provide insights into the active sites and pathways that control oxidation over Au/TiO2 catalysts. We provide transmission IR spectroscopic data that show the direct involvement of the Au-Ti(4+) dual perimeter sites, and density functional theory results that connect the electronic properties at these sites to their reactivity and to plausible reaction mechanisms. We also show the importance of interfacial Au-Ti(4+) sites in adsorbing and activating O2 as a result of charge transfer from the Au into antibonding states on O2 causing di-σ interactions with interfacial Au-Ti(4+) sites. This results in apparent activation energies for O2 activation of 0.16-0.60 eV thus allowing these materials to operate over a wide range of temperatures (110-420 K) and offering the ability also to control H-H, C-H, and C-O bond scission. At low temperatures (100-130 K), adsorbed O2 directly reacts with co-adsorbed CO or H2. In addition, we observe the specific consumption of CO adsorbed on TiO2. The more strongly held CO/Au species do not react at ∼120 K due to high diffusion barriers that prevent them from reaching active interfacial sites. At higher temperatures, O2 directly dissociates to form active oxygen adatoms (O*) on Au and TiO2. These readily react with bound hydrocarbon intermediates via base-catalyzed nucleophilic attack on unsaturated C═O and C═C bonds or via activation of weakly acidic C-H or O-H bonds. We

  3. Rapid Access to Ortho-Alkylated Vinylarenes from Aromatic Acids by Dearomatization and Tandem Decarboxylative C-H Olefination/Rearomatization. (United States)

    Tsai, Hung-Chang; Huang, Yen-Hsiang; Chou, Chih-Ming


    A two-step straightforward method for the preparation of ortho-alkylated vinylarenes from readily available benzoic acids is described. The synthetic route involves the dearomatization of benzoic acids by Birch reduction providing alkylated cyclohexa-2,5-dienyl-1-carboxylic acids. The diene subsequently undergoes a decarboxylative C-H olefination followed by rearomatization to deliver ortho-alkylated vinylarene. Mechanistic studies suggest that a Pd/Ag bimetallic catalytic system is important in the tandem decarboxylative C-H olefination/rearomatization step.

  4. Investigation of the structure and properties of a-C:H coatings with metal and silicon containing interlayers (United States)

    Nöthe, M.; Breuer, U.; Koch, F.; Penkalla, H. J.; Rehbach, W. P.; Bolt, H.


    The structure of the interface of a-C:H coatings deposited with metal and Si-containing interlayers has been studied. Carbide forming metals (Al, Ti, Cr) can improve the chemical bonding compared with a substrate material which does not form carbides extensively by itself. In addition, a graded transition zone enlarges the interface between the carbon layer and the interlayer metal. In the present work the metal atoms were evaporated and ionized into a dense Ar plasma and deposited onto Si (100) substrates. A graded interface between the metal interlayer and the a-C:H coating was produced by introducing C 2H 2 with increasing amount into the Ar/He plasma during the PAPVD metal deposition process. The PACVD a-C:H deposition process was continued after the termination of metal evaporation to produce the pure a-C:H top layer. Further to Al-, Cr-, Ti- and Cu-interlayers, Si-containing interlayers were investigated. The Si-containing interlayers were deposited by a PACVD process using tetraethoxysilane Si(OC 2H 5) 4 (TEOS) and tetramethylsilane Si(CH 3) 4 (TMS). The characterization of the deposited layer systems was performed by SIMS, SNMS and XPS analyses as well as SEM and analytical TEM methods.

  5. Influence of nitrogen on the tribological properties of a-C:H layers on the polycarbonate substrates

    Directory of Open Access Journals (Sweden)

    Rafal M. Nowak


    Full Text Available Polycarbonate (PC possesses many commercial applications. However, PC is still limited to non-abrasive and chemical-free environments due to its low hardness, low scratching resistance and high susceptibility to chemical attacks. To overcome this limitation, PC can be coated by hydrogenated amorphous carbon layers. The a-C:H layers have very attractive properties such as high hardness, infrared transparency, chemical inertness, low friction coefficients, and biocompatibility. Addition of nitrogen in the structure allows lowering internal stress and improve tribological properties of a-C:H layers. In this work, a-C:N:H layers were deposited from mixture CH4/N2 gases by RF PECVD method. Effects of the nitrogen incorporation on structure and tribological properties of deposited layers were investigated. The structure of layers were characterized by Fourier Transform Infrared spectroscopy (FTIR and X-ray photoelectron spectroscopy (XPS. The friction coefficient, wear resistance of a-C:H:N layers were estimated by tribometer in ball-on-disc configuration. The IR spectra of the obtained layers have demonstrated a presence of nitrogen bonded both to carbon and to hydrogen. A formation of the following bonds has been confirmed: -C≡N, -NH2, -C−NH2, >C=NH. They are all typical for a-C:N:H layers. The tribological tests have shown that the layers reduce the friction coefficient of the polycarbonate (up to 50 % and considerably improve wear resistance.

  6. Direct Electrophilic C-H Alkynylation of Unprotected 2-Vinylanilines. (United States)

    Caspers, Lucien D; Finkbeiner, Peter; Nachtsheim, Boris J


    Unprotected aromatic amines can be used as directing groups in metal-catalyzed C-H alkynylations of alkenes. By using low amounts of an Ir III catalyst in combination with alkynylbenziodoxolones as electrophilic alkyne-transfer reagents, highly desirable 1,3-enynes were isolated in excellent yields of up to 98 % with Z stereoselectivity. A broad substrate scope as well as the high synthetic utility of the 1,3-enynes render this new method an efficient approach for the synthesis of five- and six-membered heterocycles. Further derivatizations of the 1,3-enynes to highly substituted quinolines through Au I - and N-bromosuccinimide-mediated exo-dig cyclizations were demonstrated. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synthesis of 2,3-Benzodiazepines via Rh(III)-Catalyzed C-H Functionalization of N-Boc Hydrazones with Diazoketoesters. (United States)

    Wang, Jie; Wang, Lili; Guo, Shan; Zha, Shanke; Zhu, Jin


    An efficient Rh(III)-catalyzed C-H activation protocol has been developed for the synthesis of 2,3-benzodiazepines with use of N-Boc hydrazones and diazoketoesters as substrates. The reaction features retention of the C═N and N-N bonds and selective cleavage of the N-Boc moiety.

  8. C-H activation of imidazolium salts by Pt(0) at ambient temperature: synthesis of hydrido platinum bis(carbene) compounds. (United States)

    Duin, Marcel A; Clement, Nicolas D; Cavell, Kingsley J; Elsevier, Cornelis J


    A zerovalent platinum(carbene) complex with two monoalkene ligands, which is able to activate C-H bonds of imidazolium salts at room temperature to yield isolable hydrido platinum(II) bis(carbene) compounds, has been synthesised for the first time.

  9. Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

    Energy Technology Data Exchange (ETDEWEB)

    T. Brent Gunnoe


    Catalysts provide foundational technology for the development of new materials and can enhance the efficiency of routes to known materials. New catalyst technologies offer the possibility of reducing energy and raw material consumption as well as enabling chemical processes with a lower environmental impact. The rising demand and expense of fossil resources has strained national and global economies and has increased the importance of accessing more efficient catalytic processes for the conversion of hydrocarbons to useful products. The goals of the research are to develop and understand single-site homogeneous catalysts for the conversion of readily available hydrocarbons into useful materials. A detailed understanding of these catalytic reactions could lead to the development of catalysts with improved activity, longevity and selectivity. Such transformations could reduce the environmental impact of hydrocarbon functionalization, conserve energy and valuable fossil resources and provide new technologies for the production of liquid fuels. This project is a collaborative effort that incorporates both experimental and computational studies to understand the details of transition metal catalyzed C-H activation and C-C bond forming reactions with olefins. Accomplishments of the current funding period include: (1) We have completed and published studies of C-H activation and catalytic olefin hydroarylation by TpRu{l_brace}P(pyr){sub 3}{r_brace}(NCMe)R (pyr = N-pyrrolyl) complexes. While these systems efficiently initiate stoichiometric benzene C-H activation, catalytic olefin hydroarylation is hindered by inhibition of olefin coordination, which is a result of the steric bulk of the P(pyr){sub 3} ligand. (2) We have extended our studies of catalytic olefin hydroarylation by TpRu(L)(NCMe)Ph systems to L = P(OCH{sub 2}){sub 3}CEt. Thus, we have now completed detailed mechanistic studies of four systems with L = CO, PMe{sub 3}, P(pyr){sub 3} and P(OCH{sub 2}){sub 3}CEt

  10. Alcohols as alkylating agents in heteroarene C?H functionalization


    Jin, Jian; MacMillan, David W. C.


    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage 1 . One of the core principles that underlies DNA biosynthesis is the radical-mediated elimnation of H2O to deoxygenate ribonucleotides, an example of ?spin-center shift? (SCS) 2 , during which an alcohol C?O bond is cleaved, resulting in a carbon-centered radical intermediate. While SCS is a well-understood biochemical process, it is underutilize...

  11. The HCClF_2-HCCH Complex: Microwave Spectrum, Structure and C-H\\cdotsπ Interactions (United States)

    Peebles, Rebecca A.; Sexton, John M.; Elliott, Ashley A.; Steber, Amanda L.; Peebles, Sean A.; Neill, Justin L.; Muckle, Matt T.; Pate, Brooks H.


    The HCF_3-HCCH complex was recently found to have a weak C-H\\cdotsπ interaction between the fluoroform and acetylene, as well as having a secondary interaction between the fluorine atoms and one of the acetylene hydrogen atoms; however, extensive splittings due to large amplitude motions within the complex have complicated our efforts at making a full assignment of the HCF_3-HCCH spectrum. In an attempt to remove some of the ambiguity in the HCF_3-HCCH study, we have substituted a chlorine atom for one fluorine atom and undertaken an investigation of the HCClF_2-HCCH complex. This eliminates the possibility of internal rotation of the methane subunit, while still maintaining a C-H\\cdotsπ interaction. Using the chirped-pulse Fourier-transform microwave (CP-FTMW) spectrometer at the University of Virginia and the Balle-Flygare FTMW spectrometer at Eastern Illinois University, the spectra of four isotopologues of HCClF_2-HCCH have been assigned, with no indication of internal motions within the complex. The structure has been determined from the experimental moments of inertia, confirming that this dimer has the expected weak C-H\\cdotsπ interaction. In addition, the off-diagonal χab quadrupole coupling constant has been used to determine the angle between the C-Cl bond and the a-axis of the complex. This, and Kraitchman coordinates for the chlorine atom, help confirm the structural details from the inertial fit. The structural results will be compared with other complexes showing C-H\\cdotsπ and C-H\\cdotsO interactions. S. A. Peebles, M. M. Serafin, R. A. Peebles, 61st International Symposium on Molecular Spectroscopy, Talk MH13, June 19, 2006.

  12. Catalytic devices

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ming; Zhang, Xiang


    This disclosure provides systems, methods, and apparatus related to catalytic devices. In one aspect, a device includes a substrate, an electrically insulating layer disposed on the substrate, a layer of material disposed on the electrically insulating layer, and a catalyst disposed on the layer of material. The substrate comprises an electrically conductive material. The substrate and the layer of material are electrically coupled to one another and configured to have a voltage applied across them.

  13. Catalytic routes to fuels from C1 and oxygenate molecules

    KAUST Repository

    Wang, Shuai


    This account illustrates concepts in chemical kinetics underpinned by the formalism of transition state theory using catalytic processes that enable the synthesis of molecules suitable as fuels from C-1 and oxygenate reactants. Such feedstocks provide an essential bridge towards a carbon-free energy future, but their volatility and low energy density require the formation of new C-C bonds and the removal of oxygen. These transformations are described here through recent advances in our understanding of the mechanisms and site requirements in catalysis by surfaces, with emphasis on enabling concepts that tackle ubiquitous reactivity and selectivity challenges. The hurdles in forming the first C-C bond from C-1 molecules are illustrated by the oxidative coupling of methane, in which surface O-atoms form OH radicals from O-2 and H2O molecules. These gaseous OH species act as strong H-abstractors and activate C-H bonds with earlier transition states than oxide surfaces, thus rendering activation rates less sensitive to the weaker C-H bonds in larger alkane products than in CH4 reactants. Anhydrous carbonylation of dimethyl ether forms a single C-C bond on protons residing within inorganic voids that preferentially stabilize the kinetically-relevant transition state through van der Waals interactions that compensate for the weak CO nucleophile. Similar solvation effects, but by intrapore liquids instead of inorganic hosts, also become evident as alkenes condense within MCM-41 channels containing isolated Ni2+ active sites during dimerization reactions. Intrapore liquids preferentially stabilize transition states for C-C bond formation and product desorption, leading to unprecedented reactivity and site stability at sub-ambient temperatures and to 1-alkene dimer selectivities previously achieved only on organometallic systems with co-catalysts or activators. C-1 homologation selectively forms C-4 and C-7 chains with a specific backbone (isobutane, triptane) on solid

  14. A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds. (United States)

    Scamp, Ryan J; Jirak, James G; Dolan, Nicholas S; Guzei, Ilia A; Schomaker, Jennifer M


    The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon-hydrogen (C-H) bond amination of activated secondary C-H bonds over tertiary alkyl C(sp(3))-H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C-H bonds over tertiary alkyl C(sp(3))-H bonds.

  15. Metal modified tungsten carbide (WC) for catalytic and electrocatalytic applications (United States)

    Mellinger, Zachary J.

    that the binding energies for methanol and methoxy as well as ethanol and ethoxy on one monolayer (ML) Pd/WC are more similar to Pd than to WC. This predicts that the ML Pd/WC surface should have catalytic properties more similar to Pd than to WC. Ultra--high vacuum (UHV) experiments were then performed to determine the reaction products and pathways for methanol and ethanol on Pd(111), WC, and Pd/WC surfaces. These studies showed that the WC surface was very active toward the O--H bond cleavage to produce a methoxy intermediate, although WC was also undesirable because it was active for C--O bond scission and less active for the C--H bond scission. Adding Pd on WC enhanced the scission of the C--H bonds of methoxy while removing the C--O bond scission reaction pathway, suggesting a synergistic effect of using Pd/WC as electrocatalysts for methanol and ethanol decomposition. Dissociation of water, which is important for CO tolerance, was also investigated using UHV techniques with the conclusion that both the WC and Pd/WC surfaces dissociated water. The predictions from UHV studies was verified in electrochemical experiments using cyclic voltammetry (CV) and chronoamperometry (CA) measurements of electro--oxidation of methanol and ethanol in an alkaline environment. These experiments showed that Pd/WC was electrochemically active towards methanol and ethanol decomposition and has greater electrochemical stability over time than pure Pd, potentially due to higher CO tolerance for Pd/WC.

  16. 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)

  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. Study of the hydrogen behavior in amorphous hydrogenated materials of type a - C:H and a - SiC:H facing fusion reactor plasma

    International Nuclear Information System (INIS)

    Barbier, G.


    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)

  19. 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.

  20. Hydrogen-bonding catalysis of sulfonium salts


    Kaneko, Shiho; Kumatabara, Yusuke; Shimizu, Shoichi; Maruoka, Keiji; Shirakawa, Seiji


    Although quaternary ammonium and phosphonium salts are known as important catalysts in phase-transfer catalysis, the catalytic ability of tertiary sulfonium salts has not yet been well demonstrated. Herein, we demonstrate the catalytic ability of trialkylsulfonium salts as hydrogen-bonding catalysts on the basis of the characteristic properties of the acidic α hydrogen atoms on alkylsulfonium salts.

  1. Recent advances in the ruthenium(ii)-catalyzed chelation-assisted C-H olefination of substituted aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway. (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani


    The transition-metal-catalyzed chelation-assisted alkenylation at the inert C-H bond of aromatics with alkenes is one of the efficient methods to synthesize substituted vinylarenes in a highly regio- and stereoselective manner. Palladium, rhodium and ruthenium complexes are frequently used as catalysts for this type of transformation. The present review describes the recent advances in the ruthenium-catalyzed chelation-assisted alkenylation at the C-H bond of aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway. Several directing groups including 2-pyridyl, carbonyl, amidine, amide, amine, imidate, sulphonic acid, triazole, cyano, oxazolidinone and hydontoin are widely used in the reaction. The scope, limitation and mechanistic investigation of the alkenylation reactions are discussed elaborately. This feature article includes all the reported ruthenium-catalyzed alkenylation reactions via the deprotonation pathway until the end of March 2017.

  2. Synthetic applications of Pd(II)-catalyzed C-H carboxylation and mechanistic insights: expedient routes to anthranilic acids, oxazolinones, and quinazolinones. (United States)

    Giri, Ramesh; Lam, Jonathan K; Yu, Jin-Quan


    A Pd(II)-catalyzed reaction protocol for the carboxylation of ortho-C-H bonds in anilides to form N-acyl anthranilic acids has been developed. This reaction procedure provides a novel and efficient strategy for the rapid assembly of biologically and pharmaceutically significant molecules, such as benzoxazinones and quinazolinones, from simple anilides without installing and removing an external directing group. The reaction conditions are also amenable to the carboxylation of N-phenyl pyrrolidinones. A monomeric palladacycle containing p-toluenesulfonate as an anionic ligand has been characterized by X-ray crystallography, and the crucial role of p-toluenesulfonic acid in the activation of C-H bonds in the presence of carbon monoxide is discussed. Identification of two key intermediates, a mixed anhydride and benzoxazinone formed by reductive elimination from organometallic Ar(CO)Pd(II)-OTs species, provides mechanistic evidence for a dual-reaction pathway.

  3. 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.

  4. Palladium-catalyzed intramolecular asymmetric C-H functionalization/cyclization reaction of metallocenes: an efficient approach toward the synthesis of planar chiral metallocene compounds. (United States)

    Deng, Ruixian; Huang, Yunze; Ma, Xinna; Li, Gencheng; Zhu, Rui; Wang, Bin; Kang, Yan-Biao; Gu, Zhenhua


    A palladium-catalyzed asymmetric synthesis of planar chiral metallocene compounds is reported. The reaction stereoselectively functionalized one of the ortho C-H bonds of Cp rings by intramolecular cyclization to form indenone derivatives in high yields with excellent enantioselectivity. The mild set of reaction conditions allowed a wide variety of chiral metallocene compounds to be synthesized with broad functional group tolerance. The influences of preinstalled chiralities on the other Cp-ring were also investigated.

  5. Polycyclization Enabled by Relay Catalysis: One-Pot Manganese-Catalyzed C-H Allylation and Silver-Catalyzed Povarov Reaction. (United States)

    Chen, Shi-Yong; Li, Qingjiang; Liu, Xu-Ge; Wu, Jia-Qiang; Zhang, Shang-Shi; Wang, Honggen


    In this study, a Mn I /Ag I -based relay catalysis process is described for the one-pot synthesis of polycyclic products by a formal [3+2] and [4+2] cycloaddition reaction cascade. A manganese(I) complex catalyzed the first example of directed C-H allylation with allenes, setting the stage for an in situ Povarov cyclization catalyzed by silver(I). The reaction proceeds with high bond-forming efficiency (three C-C bonds), broad substrate scope, high regio- and stereoselectivity, and 100 % atom economy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Pyrroloindolone synthesis via a Cp*Co(III)-catalyzed redox-neutral directed C-H alkenylation/annulation sequence. (United States)

    Ikemoto, Hideya; Yoshino, Tatsuhiko; Sakata, Ken; Matsunaga, Shigeki; Kanai, Motomu


    A unique synthetic utility of a Cp*Co(III) catalyst in comparison with related Cp*Rh(III) catalysts is described. A C2-selective indole alkenylation/annulation sequence proceeded smoothly with catalytic amount of a [Cp*Co(III)(C6H6)](PF6)2 complex and KOAc. Intramolecular addition of an alkenyl-Cp*Co species to a carbamoyl moiety gave pyrroloindolones in 58-89% yield in one pot. Clear difference was observed between the catalytic activity of the Cp*Co(III) complex and those of Cp*Rh(III) complexes, highlighting the unique nucleophilic activity of the organocobalt species. The Cp*Co(III) catalysis was also suitable for simple alkenylation process of N-carbamoyl indoles, and broad range of alkynes, including terminal alkynes, were applicable to give C2-alkenylated indoles in 50-99% yield. Mechanistic studies on C-H activation step under Cp*Co(III) catalysis with the aid of an acetate unit as well as evaluation of the difference between organo-Co(III) species and organo-Rh(III) species are also described.

  7. Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling. (United States)

    Deb, Arghya; Hazra, Avijit; Peng, Qian; Paton, Robert S; Maiti, Debabrata


    Directing group-assisted regioselective C-H olefination with electronically biased olefins is well studied. However, the incorporation of unactivated olefins has remained largely unsuccessful. A proper mechanistic understanding of olefination involving unactivated alkenes is therefore essential for enhancing their usage in future. In this Article, detailed experimental and computational mechanistic studies on palladium catalyzed C-H olefination with unactivated, aliphatic alkenes are described. The isolation of Pd(II) intermediates is shown to be effective for elucidating the elementary steps involved in catalytic olefination. Reaction rate and order determination, control experiments, isotopic labeling studies, and Hammett analysis have been used to understand the reaction mechanism. The results from these experimental studies implicate β-hydride elimination as the rate-determining step and that a mechanistic switch occurs between cationic and neutral pathway. Computational studies support this interpretation of the experimental evidence and are used to uncover the origins of selectivity.

  8. Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters. (United States)

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


    Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or

  9. Thermodynamic design of a high temperature chemical vapor deposition process to synthesize α-SiC in Si-C-H and Si-C-H-Cl systems (United States)

    Kang, Yura; Yoo, Chang-Hyoung; Nam, Deok-Hui; Lee, Myung-Hyun; Seo, Won-Seon; Hong, Suklyun; Jeong, Seong-Min


    In this study, we thermodynamically reviewed the suitable growth process conditions of α-SiC in the Si-C-H system using tetramethylsilane (TMS) and in the Si-C-H-Cl system using methyltrichlorosilane (MTS). In the Si-C-H-Cl system, pure solid SiC was obtained at high temperatures under a larger range of hydrogen dilution ratios than that tolerated in the Si-C-H system. X-ray diffraction and micro-Raman analysis of the products obtained at 1900, 2000, and 2100 °C showed that the α-SiC becomes more dominant with increasing temperature in the Si-C-H-Cl system. While TMS was unsuitable for high temperature processing due to its high C/Si ratio, MTS was found to be appropriate for growing α-SiC crystals at high temperatures under a range of conditions. These results indicate that a novel method to grow α-SiC single crystals through HTCVD using MTS as a precursor could be established.

  10. 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)

  11. Breakdown of the Coulomb friction law in TiC/a-C : H nanocomposite coatings

    NARCIS (Netherlands)

    Pei, Y.T.; Huizenga, P.; 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-1000 or HTC 1200). In this paper, we report on the tribological behavior of TiC/a-C:H nanocomposite coatings in which ultralow friction is

  12. Influence of nitrogen doping on different properties of a-C : H

    NARCIS (Netherlands)

    Hauert, R.; Glisenti, A.; Metin, S.; Goitia, J.; Kaufman, J.H.; Loosdrecht, P.H.M. van; Kellock, A.J.; Hoffmann, P.; White, R.L.; Hermsmeier, B.D.


    Amorphous hydrogenated carbon (a-C:H) exhibits outstanding properties such as high hardness, low mechanical wear and friction, high thermal conductivity, etc. These properties are irreversibly altered above 400 °C. Doping the a-C:H films with nitrogen revealed the possibility to continuously tune

  13. Pd(II)-Catalyzed Enantioselective C-H Olefination of Diphenylacetic Acids (United States)

    Shi, Bing-Feng; Zhang, Yang-Hui; Lam, Jonathan K.; Wang, Dong-Hui; Yu, Jin-Quan


    Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of mono-protected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate. PMID:20017549

  14. 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

  15. Aging of oxygen and hydrogen plasma discharge treated a-C:H and ta-C coatings (United States)

    Bachmann, Svenja; Schulze, Marcus; Morasch, Jan; Hesse, Sabine; Hussein, Laith; Krell, Lisa; Schnagl, Johann; Stark, Robert W.; Narayan, Suman


    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 (O2) and hydrogen (H2) 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 H2 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 influenced by the environmental conditions.

  16. Atroposelective Synthesis of Axially Chiral Biaryls by Palladium-Catalyzed Asymmetric C-H Olefination Enabled by a Transient Chiral Auxiliary. (United States)

    Yao, Qi-Jun; Zhang, Shuo; Zhan, Bei-Bei; Shi, Bing-Feng


    Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C-H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98 %) with excellent enantioselectivities (95 to >99 % ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99 % ee, s-factor up to 600). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Thin films of hydrogenated amorphous carbon (a-C:H) obtained through chemical vapor deposition assisted by plasma

    International Nuclear Information System (INIS)

    Mejia H, J.A.; Camps C, E.E.; Escobar A, L.; Romero H, S.; Chirino O, S.; Muhl S, S.


    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 2 /CH 4 in relationship of 80/20 and 95/05 as precursory gases, with work pressures of 4X10 -4 to 6x10 -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)

  18. Electronic and Steric Tuning of a Prototypical Piano Stool Complex: Rh(III) Catalysis for C-H Functionalization. (United States)

    Piou, Tiffany; Rovis, Tomislav


    The history of transition metal catalysis is heavily steeped in ligand design, clearly demonstrating the importance of this approach. The intimate relationship between metal and ligand can profoundly affect the outcome of a reaction, often impacting selectivity, physical properties, and the lifetime of a catalyst. Importantly, this metal-ligand relationship can provide near limitless opportunities for reaction discovery. Over the past several years, transition-metal-catalyzed C-H bond functionalization reactions have been established as a critical foundation in organic chemistry that provides new bond forming strategies. Among the d-block elements, palladium is arguably one of the most popular metals to accomplish such transformations. One possible explanation for this achievement could be the broad set of phosphine and amine based ligands available in the chemist's toolbox compatible with palladium. In parallel, other metals have been investigated for C-H bond functionalization. Among them, pentamethylcyclopentadienyl (Cp*) Rh(III) complexes have emerged as a powerful mode of catalysis for such transformations providing a broad spectrum of reactivity. This approach possesses the advantage of often very low catalyst loading, and reactions are typically performed under mild conditions allowing broad functional group tolerance. Cp*Rh(III) is considered as a privileged catalyst and a plethora of reactions involving a C-H bond cleavage event have been developed. The search for alternative cyclopentadienyl based ligands has been eclipsed by the tremendous effort devoted to exploring the considerable scope of reactions catalyzed by Cp*Rh(III) complexes, despite the potential of this strategy for enabling reactivity. Thus, ligand modification efforts in Rh(III) catalysis have been an exception and research directed toward new rhodium catalysts has been sparse. Recently, chiral cyclopentadienyl ligands have appeared allowing enantioselective Rh(III)-catalyzed C-H

  19. On the catalytic gas phase oxidation of butadiene to furan

    Energy Technology Data Exchange (ETDEWEB)

    Kubias, B.; Rodemerck, U. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany); Ritschl, F.; Meisel, M. [Humboldt-Universitaet, Berlin (Germany). Inst. fuer Chemie


    Applying the thermochemical selectivity criterion of Hadnett et al. It is shown that the selectivity of the furan formation is not limited by a too low strength of the C-H bonds in furan when compared with the C-H bond dissociation energy in the educt molecule butadiene. In the oxidation of butadiene on a CsH{sub 2}PMo{sub 12}O{sub 40} catalyst a maximum yield of 22 mol% furan has been obtained. To improve this comparatively low furan yield oxidation activity of the catalyst must be lowered to prevent the consecutive reaction to maleic anhydride. (orig.)

  20. Oxidation of phosphine by sulfur or selenium involving a catalytic ...

    Indian Academy of Sciences (India)


    P NMR spec- troscopy. Such interconversion with the participation of breaking of bridging copper-µ3-sulfur bond with the formation of new copper–phosphorous bond led to the development of a catalytic cycle using excess. PPh3 and S or Se as the reacting substrates. The turnover number for the oxidation of PPh3 by S ...

  1. Oxidation of phosphine by sulfur or selenium involving a catalytic ...

    Indian Academy of Sciences (India)


    sulfur bond with the formation of new copper–phosphorous bond led to the development of a catalytic cycle using excess. PPh3 and S or Se as the reacting ... clean inter conversion between tetramer and monomer complex using elemental sulfur ...

  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. Chemical and morphological difference between TiN/DLC and a-C:H/DLC grown by pulsed vacuum arc techniques

    Energy Technology Data Exchange (ETDEWEB)

    Castillo, H.A. [Laboratorio de Fisica del Plasma, Universidad Nacional de Colombia Sede Manizales, Manizales (Colombia); Restrepo-Parra, E., E-mail: [Laboratorio de Fisica del Plasma, Universidad Nacional de Colombia Sede Manizales, Manizales (Colombia); Arango-Arango, P.J. [Laboratorio de Fisica del Plasma, Universidad Nacional de Colombia Sede Manizales, Manizales (Colombia)


    In order to improve the adherence of DLC films, interlayers of amorphous hydrogenated carbon (a-C:H) and titanium nitride (TiN) were deposited by means of the pulsed vacuum arc technique. Bilayers were obtained by using a carbon target of 99.98% of purity in mixtures of (Ar + CH{sub 4}) and (Ar + H{sub 2}) for producing a-C and DLC, respectively and a target of titanium of 99.999% in a mixture of (Ar + N{sub 2}) for growing TiN. After the deposition, chemical and morphological differences between TiN/DLC and a-C:H/DLC bilayers grown on silicon and stainless steel 304 were studied using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and scanning probe microscopy (SPM) techniques. XPS analysis showed a difference in sp{sup 3}/(sp{sup 2}+sp{sup 3}) bonds ratio for each bilayer, being 0.67 for TiN/DLC and 0.45 for a-C:H/DLC bilayers. sp{sup 3} and sp{sup 2} bonds were also observed by the FTIR technique. SPM images, in atomic force microscopy (AFM) and lateral force microscopy (LFM) modes were carried out for illustrating the comparison between TiN/DLC and a-C/DLC morphologic characteristics. Roughness and grain size were studied as a function of the H{sub 2} concentration for both bilayers.

  4. Infrared spectroscopy and Density Functional Theory of crystalline β-2,4,6,8,10,12-hexanitrohexaaziosowurtzitane (β CL-20) in the region of its C-H stretching vibrations. (United States)

    Behler, K D; Pesce-Rodriguez, R; Cabalo, J; Sausa, R


    Molecular vibrational spectroscopy provides a useful tool for material characterization and model verification. We examine the CH stretching fundamental and overtones of energetic material β-2,4,6,8,10,12-hexanitrohexaaziosowurtzitane (β-CL-20) by Raman spectroscopy, Fourier Transform Infrared Spectroscopy, and Laser Photoacoustic Overtone Spectroscopy, and utilize Density Functional Theory to calculate the C-H bond energy of β-CL-20 in a crystal. The spectra reveal four intense and distinct features, whose analysis yields C-H stretching fundamental frequencies and anharmonicity values that range from 3137 to 3170 cm(-1) and 53.8 to 58.8 cm(-1), respectively. From these data, we estimate an average value of 42,700 cm(-1) (5.29 eV) for the C-H bond energy, a value that agrees with our quantum mechanical calculations. Published by Elsevier B.V.

  5. Iridium/Bipyridine-Catalyzed ortho-Selective C-H Borylation of Phenol and Aniline Derivatives. (United States)

    Li, Hong-Liang; Kanai, Motomu; Kuninobu, Yoichiro


    An iridium-catalyzed ortho-selective C-H borylation of phenol and aniline derivatives has been successfully developed. Iridium/bipyridine-catalyzed C-H borylation generally occurred at the meta- and para-positions of aromatic substrates. Introduction of an electron-withdrawing substituent on the bipyridine-type ligand and a methylthiomethyl group on the hydroxy and amino groups of the phenol and aniline substrates, however, dramatically altered the regioselectivity, affording exclusively ortho-borylated products. The reaction proceeded in good to excellent yields with good functional group tolerance. C-H borylation was applied to the synthesis of a calcium receptor modulator.

  6. [Ru(TPP)CO]-catalysed intramolecular benzylic C-H bond amination, affording phenanthridine and dihydrophenanthridine derivatives. (United States)

    Intrieri, Daniela; Mariani, Matteo; Caselli, Alessandro; Ragaini, Fabio; Gallo, Emma


    Shedding light on azides: [Ru(TPP)CO] (TPP=tetraphenyl porphyrin dianion), white light and O(2) were found to be a suitable catalyst combination to perform the annulation of several biaryl azides. The high chemoselectivity of the process allows the synthesis of phenanthridines and dihydrophenanthridines in good yield and purity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 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.

  8. 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...

  9. The preparation and mechanical properties of Al-containing a-C : H thin films

    International Nuclear Information System (INIS)

    Zhang Guangan; Yan Pengxun; Wang Peng; Chen Youming; Zhang Junyan


    Al-containing hydrogenated amorphous carbon (Al-C : H) films were deposited on silicon substrates using a mid frequency magnetron sputtering Al target in an argon and methane gas mixture. The composition, surface morphology, hardness and friction coefficient of the films were characterized using x-ray photoelectron spectroscopy, atomic force microscopy, nanoindentation and tribological tester. The Al-C : H films deposited at low CH 4 content show high surface roughness, low hardness and high friction coefficient, similar to metallic Al films; in contrast, the Al-C : H films prepared under high CH 4 content indicate low surface roughness, high hardness and low friction coefficient, close to that of hard a-C : H films as wear-resistance films

  10. 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.

  11. Palladium-Catalyzed C-H Arylation of 1,2,3-Triazoles. (United States)

    Zhang, Chengwei; You, Lin; Chen, Chuo


    Palladium(II) acetate, in combination with triphenylphosphine, catalyzes direct arylation of 1,4-disubstituted 1,2,3-triazoles effectively. This C-H arylation reaction provides facile access to fully substituted triazoles with well-defined regiochemistry.

  12. 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...

  13. Palladium catalyzed selective distal C-H olefination of biaryl systems. (United States)

    Maity, Soham; Hoque, Ehtasimul; Dhawa, Uttam; Maiti, Debabrata


    Palladium catalyzed selective distal C-H activation with nitrile based templates has been of significant research interest in recent times. In this report, we disclose the distal C-H olefination of biphenyl systems with high regio- and stereo-selectivity and useful synthetic yields. The utility of this method has been demonstrated through its wide olefin scope, its operation at the gram scale and the easy removal/recovery of the directing group.

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


    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 substrate bias or carbon content. Micro-cracks induced by nanoindentation or wear tests readily propagate through the column boundaries whereas the coatings without a columnar inicrostructure exhibit s...

  15. 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.

  16. Hydrogen Bonds and Life in the Universe. (United States)

    Vladilo, Giovanni; Hassanali, Ali


    The scientific community is allocating more and more resources to space missions and astronomical observations dedicated to the search for life beyond Earth. This experimental endeavor needs to be backed by a theoretical framework aimed at defining universal criteria for the existence of life. With this aim in mind, we have explored which chemical and physical properties should be expected for life possibly different from the terrestrial one, but similarly sustained by genetic and catalytic molecules. We show that functional molecules performing genetic and catalytic tasks must feature a hierarchy of chemical interactions operating in distinct energy bands. Of all known chemical bonds and forces, only hydrogen bonds are able to mediate the directional interactions of lower energy that are needed for the operation of genetic and catalytic tasks. For this reason and because of the unique quantum properties of hydrogen bonding, the functional molecules involved in life processes are predicted to have extensive hydrogen-bonding capabilities. A molecular medium generating a hydrogen-bond network is probably essential to support the activity of the functional molecules. These hydrogen-bond requirements constrain the viability of hypothetical biochemistries alternative to the terrestrial one, provide thermal limits to life molecular processes, and offer a conceptual framework to define a transition from a "covalent-bond stage" to a "hydrogen-bond stage" in prebiotic chemistry.

  17. Hydrogen Bonds and Life in the Universe (United States)


    The scientific community is allocating more and more resources to space missions and astronomical observations dedicated to the search for life beyond Earth. This experimental endeavor needs to be backed by a theoretical framework aimed at defining universal criteria for the existence of life. With this aim in mind, we have explored which chemical and physical properties should be expected for life possibly different from the terrestrial one, but similarly sustained by genetic and catalytic molecules. We show that functional molecules performing genetic and catalytic tasks must feature a hierarchy of chemical interactions operating in distinct energy bands. Of all known chemical bonds and forces, only hydrogen bonds are able to mediate the directional interactions of lower energy that are needed for the operation of genetic and catalytic tasks. For this reason and because of the unique quantum properties of hydrogen bonding, the functional molecules involved in life processes are predicted to have extensive hydrogen-bonding capabilities. A molecular medium generating a hydrogen-bond network is probably essential to support the activity of the functional molecules. These hydrogen-bond requirements constrain the viability of hypothetical biochemistries alternative to the terrestrial one, provide thermal limits to life molecular processes, and offer a conceptual framework to define a transition from a “covalent-bond stage” to a “hydrogen-bond stage” in prebiotic chemistry. PMID:29301382

  18. 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.

  19. 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 AgSbF 6 , 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)] + , AgSbF 6 , in which SbF 6 - 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 AgSbF 6 , and this facilitates the first alkyne insertion; and (ii) a rhodium-carbene is easily formed.

  20. The mechanism of stereospecific C-H oxidation by Fe(Pytacn) complexes: bioinspired non-heme iron catalysts containing cis-labile exchangeable sites. (United States)

    Prat, Irene; Company, Anna; Postils, Verònica; Ribas, Xavi; Que, Lawrence; Luis, Josep M; Costas, Miquel


    A detailed mechanistic study of the hydroxylation of alkane C-H bonds using H2O2 by a family of mononuclear non heme iron catalysts with the formula [Fe(II)(CF3SO3)2(L)] is described, in which L is a tetradentate ligand containing a triazacyclononane tripod and a pyridine ring bearing different substituents at the α and γ positions, which tune the electronic or steric properties of the corresponding iron complexes. Two inequivalent cis-labile exchangeable sites, occupied by triflate ions, complete the octahedral iron coordination sphere. The C-H hydroxylation mediated by this family of complexes takes place with retention of configuration. Oxygen atoms from water are incorporated into hydroxylated products and the extent of this incorporation depends in a systematic manner on the nature of the catalyst, and the substrate. Mechanistic probes and isotopic analyses, in combination with detailed density functional theory (DFT) calculations, provide strong evidence that C-H hydroxylation is performed by highly electrophilic [Fe(V)(O)(OH)L] species through a concerted asynchronous mechanism, involving homolytic breakage of the C-H bond, followed by rebound of the hydroxyl ligand. The [Fe(V)(O)(OH)L] species can exist in two tautomeric forms, differing in the position of oxo and hydroxide ligands. Isotopic-labeling analysis shows that the relative reactivities of the two tautomeric forms are sensitively affected by the α substituent of the pyridine, and this reactivity behavior is rationalized by computational methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. An electron spectroscopy study of a-C:H films produced by PACVD in a CH 4-CO 2 gas mixture (United States)

    Calliari, L.; Filippi, M.; Gottardi, G.; Laidani, N.; Anderle, M.


    The near surface region microstructure of a PACVD a-C:H film is investigated by probing the occupied electron states by electron energy loss spectroscopy (EELS) in the low loss region, C KVV Auger emission, C 1s photoemission, X-ray and UV excited valence band (VB) photoemission. The film, deposited under pulsed bias voltage, is described as a hydrogenated amorphous carbon material, possibly involving a small amount (a few at.%) of oxygen. The C electron states are dominantly sp 3 hybridized, with H stabilizing the associated tetrahedral bond. A maximum of ≈35% sp 2 bonded carbons exists in the system. The sp 2 sites do not gather into extended π bonded graphite-like structures, thereby allowing the existence of a large (⩾1.8 eV) energy gap. The presence of H explains the mass density (≈1.7 g/cm 3) and hardness (≈10 GPa) of the film which both classify it, in spite of the high sp 3 fraction, at the border between soft and hard a-C:H materials.

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


    Leoni Villano Bonamin; Lucienne Colombo Martini; Fernanda Martins Soares; Marcos Paulo da Silva Rocha


    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...

  3. 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.

  4. 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)


    International Nuclear Information System (INIS)



    This research program is directed at obtaining detailed experimental information on the electronic interactions between metals and organic molecules. These interactions provide low energy pathways for many important chemical and catalytic processes. A major feature of the program is the continued development and application of our special high-resolution valence photoelectron spectroscopy (UPS), and high-precision X-ray core photoelectron spectroscopy (XPS) instrumentation for study of organometallic molecules in the gas phase. The study involves a systematic approach towards understanding the interactions and activation of bound carbonyls, C-H bonds, methylenes, vinylidenes, acetylides, alkenes, alkynes, carbenes, carbynes, alkylidenes, alkylidynes, and others with various monometal, dimetal, and cluster metal species. Supporting ligands include -aryls, alkoxides, oxides, and phosphines. We are expanding our studies of both early and late transition metal species and electron-rich and electron-poor environments in order to more completely understand the electronic factors that serve to stabilize particular organic fragments and intermediates on metals. Additional new directions for this program are being taken in ultra-high vacuum surface UPS, XPS, scanning tunneling microscopy (STM) and atomic force microscopy (AFM) experiments on both physisorbed and chemisorbed organometallic thin films. The combination of these methods provides additional electronic structure information on surface-molecule and molecule-molecule interactions. A very important general result emerging from this program is the identification of a close relationship between the ionization energies of the species and the thermodynamics of the chemical and catalytic reactions of these systems


    Energy Technology Data Exchange (ETDEWEB)



    This research program is directed at obtaining detailed experimental information on the electronic interactions between metals and organic molecules. These interactions provide low energy pathways for many important chemical and catalytic processes. A major feature of the program is the continued development and application of our special high-resolution valence photoelectron spectroscopy (UPS), and high-precision X-ray core photoelectron spectroscopy (XPS) instrumentation for study of organometallic molecules in the gas phase. The study involves a systematic approach towards understanding the interactions and activation of bound carbonyls, C-H bonds, methylenes, vinylidenes, acetylides, alkenes, alkynes, carbenes, carbynes, alkylidenes, alkylidynes, and others with various monometal, dimetal, and cluster metal species. Supporting ligands include -aryls, alkoxides, oxides, and phosphines. We are expanding our studies of both early and late transition metal species and electron-rich and electron-poor environments in order to more completely understand the electronic factors that serve to stabilize particular organic fragments and intermediates on metals. Additional new directions for this program are being taken in ultra-high vacuum surface UPS, XPS, scanning tunneling microscopy (STM) and atomic force microscopy (AFM) experiments on both physisorbed and chemisorbed organometallic thin films. The combination of these methods provides additional electronic structure information on surface-molecule and molecule-molecule interactions. A very important general result emerging from this program is the identification of a close relationship between the ionization energies of the species and the thermodynamics of the chemical and catalytic reactions of these systems.

  7. Organocatalysis in cross-coupling: DMEDA-catalyzed direct C-H arylation of unactivated benzene. (United States)

    Liu, Wei; Cao, Hao; Zhang, Hua; Zhang, Heng; Chung, Kin Ho; He, Chuan; Wang, Haibo; Kwong, Fuk Yee; Lei, Aiwen


    A striking breakthrough to the frame of traditional cross-couplings/C-H functionalizations using an organocatalyst remains unprecedented. We uncovered a conceptually different approach toward the biaryl syntheses by using DMEDA as the catalyst to promote the direct C-H arylation of unactivated benzene in the presence of potassium tert-butoxide. The arylation of unactivated benzene with aryl iodides, or aryl bromides and even chlorides under the assistance of an iodo-group, could simply take place at 80 °C. The new methodology presumably involves an aryl radical anion as an intermediate. This finding offers an option toward establishing a new horizon for direct C-H/cross-coupling reactions.

  8. Method to produce catalytically active nanocomposite coatings

    Energy Technology Data Exchange (ETDEWEB)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat


    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  9. Method to produce catalytically active nanocomposite coatings (United States)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat


    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  10. Electrochemical C-H Amination by Cobalt Catalysis in a Renewable Solvent. (United States)

    Sauermann, Nicolas; Mei, Ruhuai; Ackermann, Lutz


    Syntheses of substituted anilines primarily rely on palladium-catalyzed coupling chemistry with prefunctionalized aryl electrophiles. While oxidative aminations have emerged as powerful alternatives, they largely produce undesired metal-containing by-products in stoichiometric quantities. In contrast, described herein is the unprecedented electrochemical C-H amination by cobalt-catalyzed C-H activation. The environmentally benign electrocatalysis avoids stoichiometric metal oxidants, can be conducted under ambient air, and employs a biomass-derived, renewable solvent for sustainable aminations in an atom- and step-economical manner with H 2 as the sole byproduct. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 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...

  12. FINAL TECHNICAL REPORT for grant DE-FG02-93ER14353 "Carbon-Hydrogen Bond Functionalization Catalyzed by Transition Metal Systems"

    Energy Technology Data Exchange (ETDEWEB)

    Goldman, Alan S


    Alkanes are our most abundant organic resource but are highly resistant to selective chemical transformations. Alkenes (olefins) by contrast are the single most versatile class of molecules for selective transformations, and are intermediates in virtually every petrochemical process as well as a vast range of commodity and fine chemical processes. Over the course of this project we have developed the most efficient catalysts to date for the selective conversion of alkanes to give olefins, and have applied these catalysts to other dehydrogenation reactions. We have also developed some of the first efficient catalysts for carbonylation of alkanes and arenes to give aldehydes. The development of these catalysts has been accompanied by elucidation of the mechanism of their operation and the factors controlling the kinetics and thermodynamics of C-H bond activation and other individual steps of the catalytic cycles. This fundamental understanding will allow the further improvement of these catalysts, as well as the development of the next generation of catalysts for the functionalization of alkanes and other molecules containing C-H bonds.

  13. 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.

  14. Mesoporous silica nanoparticles for biomedical and catalytical applications

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Xiaoxing [Iowa State Univ., Ames, IA (United States)


    Mesoporous silica materials, discovered in 1992 by the Mobile Oil Corporation, have received considerable attention in the chemical industry due to their superior textual properties such as high surface area, large pore volume, tunable pore diameter, and narrow pore size distribution. Among those materials, MCM-41, referred to Mobile Composition of Matter NO. 41, contains honeycomb liked porous structure that is the most common mesoporous molecular sieve studied. Applications of MCM-41 type mesoporous silica material in biomedical field as well as catalytical field have been developed and discussed in this thesis. The unique features of mesoporous silica nanoparticles were utilized for the design of delivery system for multiple biomolecules as described in chapter 2. We loaded luciferin into the hexagonal channels of MSN and capped the pore ends with gold nanoparticles to prevent premature release. Luciferase was adsorbed onto the outer surface of the MSN. Both the MSN and the gold nanoparticles were protected by poly-ethylene glycol to minimize nonspecific interaction of luciferase and keep it from denaturating. Controlled release of luciferin was triggered within the cells and the enzymatic reaction was detected by a luminometer. Further developments by varying enzyme/substrate pairs may provide opportunities to control cell behavior and manipulate intracellular reactions. MSN was also served as a noble metal catalyst support due to its large surface area and its stability with active metals. We prepared MSN with pore diameter of 10 nm (LP10-MSN) which can facilitate mass transfer. And we successfully synthesized an organo silane, 2,2'-Bipyridine-amide-triethoxylsilane (Bpy-amide-TES). Then we were able to functionalize LP10-MSN with bipyridinyl group by both post-grafting method and co-condensation method. Future research of this material would be platinum complexation. This Pt (II) complex catalyst has been reported for a C-H bond activation reaction as an

  15. Alkane activation at ambient temperature - Unusual selectivities, C-C, C-H bond scission vs C-C bond coupling

    NARCIS (Netherlands)

    Trionfetti, C.; Agiral, A.; Gardeniers, Han J G E; Lefferts, L.; Seshan, K.


    Availability and low cost of light alkanes make them interesting as feedstock for commercial fuels and chemicals. However, direct conversion of lower alkanes for such purposes is a challenging problem. A discussion covers the oxidative conversion of light alkanes in the presence of cold plasma in a

  16. 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

  17. 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

  18. F. H. C h . J othmann , De Bijbel in de loop der eeuwen. Kampen, J ...

    African Journals Online (AJOL)


    F. H. C h . J othmann , De Bijbel in de loop der eeuwen. Kampen, J . H. Kok. N.V., 1954, 43 bis. Prys 95 cent. Hierdie werkie geskryf vir gebruik op skool, kategesasie en jeug- vereniging is besonder smakelik versorg met uiters insiggewende illu- strasies oor die geskiedenis van die Bybel as geskrif en boek. Die stof is.

  19. Penicillin resistant gonococci at Q.E.C.H. | Ward | Malawi Medical ...

    African Journals Online (AJOL)

    Malawi Medical Journal. Journal Home · ABOUT THIS JOURNAL · Advanced Search · Current Issue · Archives · Journal Home > Vol 3, No 2 (1986) >. Log in or Register to get access to full text downloads. Username, Password, Remember me, or Register. Penicillin resistant gonococci at Q.E.C.H.. JC Ward, JS ...

  20. Breakdown of the Coulomb friction law in TiC/a-C:H nanocomposite coatings

    International Nuclear Information System (INIS)

    Pei, Y. T.; Huizenga, P.; 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-1000 or HTC 1200). In this paper, we report on the tribological behavior of TiC/a-C:H nanocomposite coatings in which ultralow friction is tailored with superior wear resistance, two properties often difficult to achieve simultaneously. Tribotests have been performed at room temperature with a ball-on-disk configuration. In situ monitoring of the wear depth of the coated disk together with the wear height of the ball counterpart at nanometer scale reveals that the self-lubricating effects are induced by the formation of transfer films on the surface of the ball counterpart. A remarkable finding is a breakdown of the Coulomb friction law in the TiC/a-C:H nanocomposite coatings. In addition, the coefficient of friction of TiC/a-C:H nanocomposite coatings decreases with decreasing relative humidity. A superior wear resistance of the coated disk at a level of 10 -17 m 3 /N m (per lap) has been achieved under the condition of superlow friction and high toughness, both of which require fine TiC nanoparticles (e.g., 2 nm) and a wide matrix separation that must be comparable to the dimensions of the nanoparticles

  1. High growth rate of a-SiC: H films using ethane carbon source by ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 36; Issue 7. High growth rate of a-SiC:H films using ethane carbon source by HW-CVD method. Mahesh M Kamble Vaishali S Waman Sanjay S Ghosh Azam Mayabadi Vasant G Sathe T Shripathi Habib M Pathan Sandesh R Jadkar. Volume 36 Issue 7 December 2013 ...

  2. 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...

  3. Cobalt-catalysed C-H carbonylative cyclisation of aliphatic amides. (United States)

    Williamson, Patrick; Galván, Alicia; Gaunt, Matthew J


    A cobalt-catalysed C-H carbonylation of aliphatic carboxamide derivatives is described, employing commercially available Co(ii)-salts in the presence of a silver oxidant. This operationally simple process utilises an atmospheric pressure of CO and generates a range of substituted succinimide products bearing diverse functional groups that can be successfully accessed via this methodology.

  4. 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.

  5. Electrochemically induced C-H functionalization using bromide ion/2,2,6,6-tetramethylpiperidinyl-N-oxyl dual redox catalysts in a two-phase electrolytic system

    International Nuclear Information System (INIS)

    Li, Chao; Zeng, Cheng-Chu; Hu, Li-Ming; Yang, Feng-Lin; Yoo, Seung Joon; Little, R. Daniel


    Highlights: •Electrocatalytic C-H bond functionalization of tetrahydroisoquinolines is reported. •The transformation is mediated by a bromide ion/TEMPO dual redox catalyst system. •The transformation is conducted in a two-phase electrolytic medium. •The mechanism is proposed to proceed via a sequence of oxidation and addition reactions involving water as a nucleophile. •The procedure features wide substrate scope, the use of mild reaction conditions. -- Abstract: The electrochemical oxidative functionalization of benzylic C-H bonds, mediated by a dual bromide ion/2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) redox catalyst system in a two-phase electrolytic medium, has been explored using cyclic voltammetry (CV) and preparative electrolysis techniques. The results show that electron transfer between TEMPO + and a neutral substrate occurs with an efficiency that depends upon the presence of a base. The preparative scale electrolysis led to the formation of dihydro-isoquinolinones, isochromanone and xanthenone in moderate to excellent yields. On the basis of the CV analysis and preparative electrolysis results, a reaction mechanism is proposed

  6. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.


    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  7. Computational Mechanistic Study of Redox-Neutral Rh(III)-Catalyzed C-H Activation Reactions of Arylnitrones with Alkynes: Role of Noncovalent Interactions in Controlling Selectivity. (United States)

    Xing, Yang-Yang; Liu, Jian-Biao; Tian, Ying-Ying; Sun, Chuan-Zhi; Huang, Fang; Chen, De-Zhan


    The mechanism of redox-neutral Rh(III)-catalyzed coupling reactions of arylnitrones with alkynes was investigated by density functional theory (DFT) calculations. The free energy profiles associated with the catalytic cycle, involving C(sp 2 )-H activation, insertion of alkyne, transfer of O atom, cyclization and protodemetalation, are presented and analyzed. An overwhelming preference for alkyne insertion into Rh-C over Rh-O is observed among all pathways, and the most favorable route is determined. The pivalate-assisted C-H activation step is turnover-limiting, and the cyclization step determines the diastereoselectivity of the reaction, with the stereoselectivity arising mainly from the difference of noncovalent interactions in key transition states. The detailed mechanism of O atom transfer, Rh III -Rh I -Rh III versus Rh III -Rh V -Rh III cycle, is discussed.

  8. Deposition of a-C:H films on a nanotrench pattern by bipolar PBII and D

    International Nuclear Information System (INIS)

    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 and 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

  9. Direct arylation of benzene with aryl bromides using high-temperature/high-pressure process windows: expanding the scope of C-H activation chemistry. (United States)

    Pieber, Bartholomäus; Cantillo, David; Kappe, C Oliver


    A detailed investigation on the direct arylation of benzene with aryl bromides by using first-row transition metals under high-temperature/high-pressure (high-T/p) conditions is described. By employing a parallel reactor platform for rapid reaction screening and discovery at elevated temperatures, various metal/ligand/base combinations were evaluated for their ability to enable biaryl formation through C-H activation. The combination of cobalt(III) acetylacetonate and lithium bis(trimethylsilyl)amide was subjected to further process intensification at 200 °C (15 bar), allowing a significant reduction of the catalyst/base loading and a dramatic increase in catalytic efficiency (turnover frequency) by a factor of 1000 compared to traditional protocols. The high-throughput screening additionally identified novel nickel- and copper-based metal/ligand combinations that favored an amination pathway competing with C-H activation, with the addition of ligands, such as 1,10-phenanthroline, having a profound influence on the selectivity. In addition to metal-based catalysts, high-T/p process windows were also successfully applied to transition-metal-free systems, utilizing 1,10-phenanthroline as organocatalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Spectroscopy of C-H stretching overtones in dimethylacetylene, dimethylcadmium, and dimethylmercury

    Energy Technology Data Exchange (ETDEWEB)

    Manzanares I., C.; Yamasaki, N.L.S.; Weitz, E. (Northwestern Univ., Evanston, IL (USA))


    The overtone spectra of a number of C-H stretching vibrations of dimethylacetylene, dimethylcadmium, and dimethylmercury were obtained by using intracavity dye laser photoacoustic spectroscopy. Transitions corresponding to the {Delta}{nu} = 5, 6, and 7 overtones of the C-H stretch are assigned by using the local-mode model. In addition, a number of local-mode-normal-mode combination bands have been identified. Local-mode harmonic frequencies ({omega}{sub e}) and anharmonicities ({omega}{sub e}x{sub e}) are obtained from Birge-Sponer plots. The line widths of the pure local-mode transitions are analyzed in terms of possible resonances with local-mode-normal-mode combination bands. Line widths in this series of compounds are compared to line widths in the M(CH{sub 3}){sub 4} and M(CH{sub 3}){sub 3} series.

  11. Selective C-H Halogenation with a Highly Fluorinated Manganese Porphyrin. (United States)

    Li, Gang; Dilger, Andrew K; Cheng, Peter T; Ewing, William R; Groves, John T


    The selective C-H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C-H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-Mn V species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Cross-Coupling Hydrogen Evolution by Visible Light Photocatalysis Toward C(sp(2))-P Formation: Metal-Free C-H Functionalization of Thiazole Derivatives with Diarylphosphine Oxides. (United States)

    Luo, Kai; Chen, Yao-Zhong; Yang, Wen-Chao; Zhu, Jie; Wu, Lei


    Visible light along with 5 mol % eosin B catalyzed the first direct C-H phosphorylation of thiazole derivatives with diarylphosphine oxides by a photoredox process in the absence of an external oxidant. The scope of thiazoles and phosphine oxides was further investigated, as was functional group tolerance. The general and operational simplicity provides a novel metal and oxidant-free alternative for the formation of heteroaryl-P bonds, and only molecular hydrogen is generated as a byproduct.

  13. Clean and efficient benzylic C-H oxidation in water using a hypervalent iodine reagent: activation of polymeric iodosobenzene with KBr in the presence of montmorillonite-K10. (United States)

    Dohi, Toshifumi; Takenaga, Naoko; Goto, Akihiro; Fujioka, Hiromichi; Kita, Yasuyuki


    We have found that unreactive and insoluble polymeric iodosobenzene [PhIO] n induced aqueous benzylic C-H oxidation to effectively give arylketones, in the presence of KBr and montmorillonite-K10 (M-K10) clay. Water-soluble and reactive species 1 having the unique I(III)-Br bond, in situ generated from [PhIO]n and KBr, was considered to be the key radical initiator during the reactions.

  14. Cobalt dinitrosoalkane complexes in the C-H functionalization of olefins. (United States)

    Schomaker, Jennifer M; Boyd, W Christopher; Stewart, Ian C; Toste, F Dean; Bergman, Robert G


    The use of cobalt dinitrosoalkane complexes in the C-H functionalization of alkenes has been demonstrated. Reaction of a series of alkenes with Me4CpCo(CO)2 in the presence of NO generates intermediate cobalt dinitrosoalkane complexes that can be deprotonated alpha to the nitrosyl group and added to various Michael acceptors. The resultant products can then undergo retrocycloaddition reactions in the presence of the original alkene to regenerate the starting cobalt dinitrosoalkane complex and release the functionalized alkene.

  15. Regioselective Annulation of Aryl Sulfonamides with Allenes through Cobalt-Promoted C-H Functionalization. (United States)

    Lan, Tianlong; Wang, Liguo; Rao, Yu


    The development of an efficient method for the construction of biologically relevant sultams is described, which represents the first case of cobalt-promoted C-H/N-H functionalization of sulfonamides with allenes. This newly developed annulation reaction demonstrated good functional group tolerance and excellent regioselectivity. Both terminal monosubstituted allenes and internal disubstituted allenes can be employed to give the desired sultams in good yields. This strategy can be successfully used to build a unique sultam library with novel structural diversity.

  16. Some growth peculiarities of a-C:H films in ECR microwavw plasma

    Czech Academy of Sciences Publication Activity Database

    Kulikovsky, V.; Shaginyan, L. R.; Jastrabík, Lubomír; Soukup, Ladislav; Boháč, Petr; Musil, Jindřich


    Roč. 60, - (2001), s. 315-323 ISSN 0042-207X R&D Projects: GA AV ČR IAA1010827 Institutional research plan: CEZ:A02/98:Z1-010-914 Keywords : a-C:H polymer-like films * ECR microwave plasma * CVD Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.541, year: 2001

  17. Synthesis of all eight L-glycopyranosyl donors using C-H activation

    DEFF Research Database (Denmark)

    Frihed, Tobias; Pedersen, Christian Marcus; Bols, Mikael


    by an intramolecular C-H activation of the methyl group in g-position; both steps were catalyzed by iridium. The following Fleming-Tamao oxidation and acetylation gave the suitably protected L-hexoses. This is the first general method for the preparation of all eight L-hexoses as their thioglycosyl donors ready...... for glycosylation and the first example of an iridium-catalyzed C(sp3)-H activation on sulfide-containing compounds....

  18. Excess C/O and C/H in Outer Protoplanetary Disk Gas (United States)

    Öberg, Karin I.; Bergin, Edwin A.


    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 compositions of the disk gas from which the envelopes are accreted. Previous models have demonstrated that sequential freeze-out of O- and C-bearing volatiles in disks will result in supersolar C/O ratios and subsolar C/H ratios in the gas between water and CO snowlines. However, this result does not take into account the expected grain growth and radial drift of pebbles in disks, and the accompanying redistribution 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 to be robust for the disk model as long as there is substantial pebble drift across the CO snowline, and the efficiency of CO vapor diffusion is limited. Gas giants that accrete their gaseous envelopes exterior to the water snowline and do not experience substantial core-envelope mixing may thus feature both superstellar C/O and C/H ratios in their atmospheres. Pebble drift will also affect the nitrogen and noble gas abundances in the planet-forming zones, which may explain some of Jupiter’s peculiar abundance patterns.

  19. Controlling the bond scission sequence of oxygenates for energy applications (United States)

    Stottlemyer, Alan L.

    The so called "Holy Grail" of heterogeneous catalysis is a fundamental understanding of catalyzed chemical transformations which span multidimensional scales of both length and time, enabling rational catalyst design. Such an undertaking is realizable only with an atomic level understanding of bond formation and destruction with respect to intrinsic properties of the metal catalyst. In this study, we investigate the bond scission sequence of small oxygenates (methanol, ethanol, ethylene glycol) on bimetallic transition metal catalysts and transition metal carbide catalysts. Oxygenates are of interest both as hydrogen carriers for reforming to H2 and CO and as fuels in direct alcohol fuel cells (DAFC). To address the so-called "materials gap" and "pressure gap" this work adopted three parallel research approaches: (1) ultra high vacuum (UHV) studies including temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) on polycrystalline surfaces; (2) DFT studies including thermodynamic and kinetic calculations; (3) electrochemical studies including cyclic voltammetry (CV) and chronoamperometry (CA). Recent studies have suggested that tungsten monocarbide (WC) may behave similarly to Pt for the electrooxidation of oxygenates. TPD was used to quantify the activity and selectivity of oxygenate decomposition for WC and Pt-modifiedWC (Pt/WC) as compared to Pt. While decomposition activity was generally higher on WC than on Pt, scission of the C-O bond resulted in alkane/alkene formation on WC, an undesired product for DAFC. When Pt was added to WC by physical vapor deposition C-O bond scission was limited, suggesting that Pt synergistically modifies WC to improve the selectivity toward C-H bond scission to produce H2 and CO. Additionally, TPD confirmed WC and Pt/WC to be more CO tolerant than Pt. HREELS results verified that surface intermediates were different on Pt/WC as compared to Pt or WC and evidence of aldehyde

  20. Catalytic distillation process (United States)

    Smith, L.A. Jr.


    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  1. Catalytic Functions of Standards

    NARCIS (Netherlands)

    K. Blind (Knut)


    textabstractThe three different areas and the examples have illustrated several catalytic functions of standards for innovation. First, the standardisation process reduces the time to market of inventions, research results and innovative technologies. Second, standards themselves promote the

  2. C-H nickellation of phenol-derived phosphinites: regioselectivity and structures of cyclonickellated complexes. (United States)

    Mangin, Loïc P; Zargarian, Davit


    This report describes the results of a study on the ortho-C-H nickellation of the aryl phosphinites i-Pr 2 P(OAr) derived from the following four groups of substituted phenols: 3-R-C 6 H 4 OH (R = F (b), Me (c), MeO (d), Cl (e)); 3,5-R 2 -C 6 H 3 OH (R = F (f), Me (g), Cl (h), OMe (i)); 2-R-C 6 H 4 OH (R = Me (j), Ph(k)); and 2,6-R 2 -C 6 H 3 OH (R = Me (l), Ph (m)). No nickellation was observed with the phosphinites derived from the 3,5-disubstituted phenols g and h, and the 2,6-disubstituted phenols l and m; in all other cases nickellation occurred at an ortho-C-H to generate either the Br-bridged dimers [{κ P ,κ C -(i-Pr) 2 POAr}Ni(μ-Br)] 2 (1b-1f, 1j, and 1k) or the monomeric acetonitrile adduct {κ P ,κ C -ArOP(i-Pr) 2 }Ni(Br)(NCMe) (1i-NCMe). Analysis of C-H nickellation regioselectivity with 3-R-C 6 H 4 OH pointed to the importance of substituent sterics, not electronics: nickellation occurred at the least hindered position either exclusively (for R = Me (c), MeO(d), and Cl (e)) or predominantly (for R = F (b); 6 : 1). This conclusion is also consistent with the observation that C-H nickellation is possible with the 3,5-disubstituted aryl phosphinites bearing F and OMe, but not with the more bulky substituents Me or Cl. For the 2-substituted aryl phosphinites, C-H nickellation occurs at the unsubstituted ortho-C-H and not on the R substituent, regardless of whether the alternative C-H moiety of the substituent is sp 3 (R = Me (j)) or sp 2 (R = Ph (k)). The system thus reveals a strong preference for formation of 5-membered metallacycles. Consistent with this reactivity, no nickellation occurs with (2,6-R 2 -C 6 H 3 O)P(i-Pr) 2 . Tests with the parent dimer derived from i-Pr 2 P(OPh) showed that conversion to the monomeric acetonitrile adduct is highly favored, going to completion with only a small excess of MeCN. All new cyclonickellated complexes reported in this study were fully characterized, including by single crystal X-ray diffraction studies

  3. Catalytic distillation structure (United States)

    Smith, L.A. Jr.


    Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

  4. Theoretical study of the catalytic desulfurization mechanism of ...

    African Journals Online (AJOL)

    The desulfurization process of compounds implicates two steps. The first step is the adsorption process on the catalytic site and the second, the breaking of the carbon-heteroatom bond leading to the heteroatom elimination. The adsorption process of thiiren have been studied and published in previous works. The results ...

  5. Development of deuterium labeling method based on the heterogeneous platinum group metal-catalyzed C-H activation. (United States)

    Sajiki, Hironao


    Deuterium (D) labeled compounds are utilized in various scientific fields such as mechanistic elucidation of reactions, preparation of new functional materials, tracers for microanalysis, deuterium labeled heavy drugs and so on. Although the H-D exchange reaction is a straightforward method to produce deuterated organic compounds, many precedent methods require expensive deuterium gas and/or harsh reaction conditions. A part of our leading research agendas is intended to the development of novel and functional heterogeneous platinum-group catalysts and the reclamation of unknown functionalities of existing heterogeneous platinum-group catalysts. During the course of the study, benzylic positions of substrates were site-selectively deuterated under mild and palladium-on-carbon (Pd/C)-catalyzed hydrogenation conditions in heavy water (D2O). Heat conditions promoted the H-D exchange reactivity and facilitated the H-D exchange reaction at not only the benzylic sites but also inactive C-H bonds and heterocyclic nuclei. It is noteworthy that platinum-on-carbon (Pt/C) indicated a quite high affinity toward aromatic nuclei, and the H-D exchange reaction was strongly enhanced by the use of Pt/C as a catalyst under milder conditions. The mixed use of Pd/C and Pt/C was found to be more efficient in the H-D exchange reaction compared to the independent use of Pd/C or Pt/C. Furthermore, simple alkanes could also be efficiently deuterated under rhodium-on-carbon (Rh/C)-catalyzed conditions. The use of ruthenium-on-carbon (Ru/C) enabled the regiospecific and efficient deuterium incorporation at α-positions of alcohols and results were applied as a regio- and stereoselective multi-deuteration method of sugar derivatives.

  6. Diffusion bonding

    International Nuclear Information System (INIS)

    Anderson, R.C.


    A method is described for joining beryllium to beryllium by diffusion bonding. At least one surface portion of at least two beryllium pieces is coated with nickel. A coated surface portion is positioned in a contiguous relationship with another surface portion and subjected to an environment having an atmosphere at a pressure lower than ambient pressure. A force is applied on the beryllium pieces for causing the contiguous surface portions to abut against each other. The contiguous surface portions are heated to a maximum temperature less than the melting temperature of the beryllium, and the applied force is decreased while increasing the temperature after attaining a temperature substantially above room temperature. A portion of the applied force is maintained at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions

  7. Tribological properties of TiC/a-C:H nanocomposite coatings prepared via HiPIMS (United States)

    Sánchez-López, J. C.; Dominguez-Meister, S.; Rojas, T. C.; Colasuonno, M.; Bazzan, M.; Patelli, A.


    High power impulse magnetron sputtering (HiPIMS) technology has been employed to prepare TiC/a-C:H nanocomposite coatings from a titanium target in acetylene (C2H2) reactive atmospheres. Gas fluxes were varied from 1.3 to 4.4 sccm to obtain C/Ti ratios from 2 to 15 as measured by electron probe microanalysis (EPMA). X-ray diffraction and transmission electron microscopy demonstrate the presence of TiC nanocrystals embedded in an amorphous carbon-based matrix. The hardness properties decrease from 17 to 10 GPa as the carbon content increases. The tribological properties were measured using a pin-on-disk tribometer in ambient air (RH = 30-40%) at 10 cm/s with 5 N of applied load against 6-mm 100Cr6 balls. The friction coefficient and the film wear rates are gradually improved from 0.3 and 7 × 10-6 mm3/N m to 0.15 and 2 × 10-7 mm3/N m, respectively, by increasing the C2H2 flux. To understand the tribological processes appearing at the interface and to elucidate the wear mechanism, microstructural and chemical investigations of the coatings were performed before and after the friction test. EPMA, X-ray photoelectron and electron energy-loss spectroscopies were employed to obtain an estimation of the fraction of the a-C:H phase, which can be correlated with the tribological behavior. Examination of the friction counterfaces (ball and track) by Raman microanalysis reveals an increased ordering of the amorphous carbon phase concomitant with friction reduction. The tribological results were compared with similar TiC/a-C(:H) composites prepared by the conventional direct current process.

  8. Photocatalytic C??H Activation of Hydrocarbons over VO@g??C3N4 (United States)

    A highly selective and sustainable method has been developed for the oxidation of methyl arenes and their analogues. The VO@g-C3N4 catalyst is very efficient in the C??H activation and oxygen insertion reaction resulting in formation of the corresponding carbonyl compounds and phenols.This dataset is associated with the following publication:Verma, S., R.B. Nasir Baig, M. Nadagouda , and R. Varma. Photocatalytic C−H Activation of Hydrocarbons over VO@g‑C3N4. ACS Sustainable Chemistry & Engineering. American Chemical Society, Washington, DC, USA, 4(4): 2333-2336, (2016).

  9. Canangalias C-H, juvenile hormone III analogues from the roots of Cananga latifolia. (United States)

    Phatchana, Ratchanee; Thongsri, Yordhathai; Yenjai, Chavi


    Chemical investigation of the roots of Cananga latifolia led to the isolation and purification of thirteen juvenile hormone III analogues. Six new analogues, canangalias C-H (1-6) and a new natural product, (2E,6E,10R)-10-acetoxy-11-hydroxy-3,7,11-trimethyldodeca-2,6-dienoic acid methyl ester (7), were isolated. In addition, six known juvenile hormone III analogues were isolated. Their structures were established by spectroscopic methods including 1D and 2D NMR, IR and mass spectrometry. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Studies of beauty baryon decays to $D^0 ph^-$ and $\\Lambda_c^+ h^-$ final states


    Aaij, Roel; Adeva, Bernardo; 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


    Decays of beauty baryons to the D[superscript 0]ph[superscript −] and Λ[+ over c]h[superscript −] 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[superscript −1], collected by the LHCb detector. The Cabibbo-suppressed decays Λ[0 over b] → D[superscript 0]pK[superscript −] and Λ[0 over b] → Λ[+ over c]K[superscript −] are observed, and their branching fractions are measured with respect to ...

  11. C-H to C-N Cross-Coupling of Sulfonamides with Olefins. (United States)

    Ma, Rulin; White, M Christina


    Cross-coupling of nitrogen with hydrocarbons under fragment coupling conditions stands to significantly impact chemical synthesis. Herein, we disclose a C(sp 3 )-N fragment coupling reaction between terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/SOX (sulfoxide-oxazoline) catalyzed intermolecular allylic C-H amination. A range of (56) allylic amines are furnished in good yields (avg. 75%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E: Z). Mechanistic studies reveal that the SOX ligand framework is effective at promoting functionalization by supporting cationic π-allyl Pd.

  12. New Approach to 1,4-Benzoxazin-3-ones by Electrochemical C-H Amination. (United States)

    Wesenberg, Lars Julian; Herold, Sebastian; Shimizu, Akihiro; Yoshida, Jun-Ichi; Waldvogel, Siegfried R


    1,4-Benzoxazin-3-ones are important structural motifs in natural products and bioactive compounds. Usually, the synthesis of benzoxazinones requires transition-metal catalysts and pre-functionalized substrates such as aryl halides. However, the anodic C-H amination of phenoxy acetates offers a very efficient and sustainable access to these heterocycles. The presented electrochemical protocol can be applied to a broad scope of alkylated substrates. Even tert-butyl moieties or halogen substituents are compatible with this versatile method. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Magnetic graphitic carbon nitride: its applicationin the C-& H-activation of amines. (United States)

    Magnetic graphitic carbon nitride, Fe@g-C3N4, has been synthesized by adorning graphitic carbon nitride (g-C3N4) support with iron oxide via non-covalent interaction. The magnetically recyclable catalyst showed excellent reactivity for expeditious C-H activation and cyanation of amines.This dataset is associated with the following publication:Verma, S., R.B. Nasir Baig, H. Changseok, M. Nadagouda , and R. Varma. Magnetic graphitic carbon nitride: its applicationin the C–H activation of amines. CHEMICAL COMMUNICATIONS. Royal Society of Chemistry, Cambridge, UK, 51(85): 15554 - 15557, (2015).

  14. 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.

  15. Structural, vibrational and bonding properties of hydro-nitrogen ...

    Indian Academy of Sciences (India)

    elongation of C-H and N-H (NH3 stretching) bonds under pressure lead to blue- and red-shift of the frequencies in the mid-IR region for TMAA and HZA ... layered energetic materials (for instance FOX-7, TATB and DAAzF) makes them ..... behavior of hydro-nitrogen solids, namely TMAA and. HZA molecular crystals, using ...

  16. 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.

  17. Rhodium mediated bond activation: from synthesis to catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Ho, Hung-An [Iowa State Univ., Ames, IA (United States)


    Recently, our lab has developed monoanionic tridentate ligand, ToR, showing the corresponding coordination chemistry and catalyst reactivity of magnesium, zirconium, zinc and iridium complexes. This thesis details synthetic chemistry, structural study and catalytic reactivity of the ToR-supported rhodium compounds. Tl[ToR] has been proved to be a superior ligand transfer agent for synthesizing rhodium complexes. The salt metathesis route of Tl[ToM] with [Rh(μ-Cl)(CO)]2 and [Rh(μ- Cl)(COE)]2 gives ToMRh(CO)2 (2.2) and ToMRhH(β3-C8H13) (3.1) respectively while Tl[ToM] with [Rh(μ-Cl)(CO)]2 affords ToPRh(CO)2 (2.3). 2.2 reacts with both strong and weak electrophiles, resulting in the oxazoline N-attacked and the metal center-attacked compounds correspondingly. Using one of the metal center-attacked electrophiles, 2.3 was demonstrated to give high diastereoselectivity. Parallel to COE allylic C-H activation complex 3.1, the propene and allylbenzene allylic C-H activation products have also been synthesized. The subsequent functionalization attempts have been examined by treating with Brønsted acids, Lewis acids, electrophiles, nucleophiles, 1,3-dipolar reagents and reagents containing multiple bonds able to be inserted. Various related complexes have been obtained under these conditions, in which one of the azide insertion compounds reductively eliminates to give an allylic functionalization product stoichiometrically. 3.1 reacts with various primary alcohols to give the decarbonylation dihydride complex ToMRh(H)2CO (4.1). 4.1 shows catalytic reactivity for primary alcohol decarbonylation under a photolytic condition. Meanwhile, 2.2 has been found to be more reactive than 4.1 for catalytic alcohol decarbonylation under the same condition. Various complexes and primary

  18. Erosion of a-B/C : H films under deuterium plasma irradiation (United States)

    Sharapov, V. M.; Kanaev, A. I.; Rybakov, S. Yu.; Gavrilov, L. E.


    The erosion of amorphous boronized carbon a-B/C : H films under low energy deuterium plasma irradiation was investigated. The films were deposited on a silicon substrate by the PCVD-method using the carborane vapour C 2B 10H 12 as a precursor. The deuterium plasma parameters in the erosion experiments were the following: ion flux density 3 × 10 16 cm -2 s -1, ion energy 50 eV, thermal atom flux density 1 × 10 16 cm -2 s -1. The erosion yields were calculated on the basis of mass thickness losses which were measured by electron probe micro-analysis. The erosion yields of a-B/C : H films do not depend on the temperature in the range 100-550°C and are more than one order of magnitude lower compared to those of boronized graphite USB-15. It was shown that the film erodes through the developing porosity which initially exists in the film and that the erosion has a chemical nature.

  19. 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.

  20. Ion beam analysis of a-C:H films on alloy steel substrate

    International Nuclear Information System (INIS)

    Silva, T.F.; Moro, M.V.; Trindade, G.F.; Added, N.; Tabacniks, M.H.; Santos, R.J.; Santana, P.L.; Bortoleto, J.R.R.


    An a-C:H thin film deposited by plasma immersion ion implantation and deposition on alloy steel (16MnCr5) was analyzed using a self-consistent ion beam analysis technique. In the self-consistent analysis, the results of each individual technique are combined in a unique model, increasing confidence and reducing simulation errors. Self-consistent analysis, then, is able to improve the regular ion beam analysis since several analyses commonly used to process ion beam data still rely on handling each spectrum independently. The sample was analyzed by particle-induced x-ray emission (for trace elements), elastic backscattering spectrometry (for carbon), forward recoil spectrometry (for hydrogen) and Rutherford backscattering spectrometry (for film morphology). The self-consistent analysis provided reliable chemical information about the film, despite its “heavy” substrate. As a result, we could determine precisely the H/C ratio, contaminant concentration and some morphological characteristics of the film, such as roughness and discontinuities. - Highlights: • Self-consistent approach of ion beam analysis was used to characterize an a-C:H film. • The self-consistent analysis provided a unequivocal and reliable model of the sample. • Morphological aspects of the film were assessed with the ion beam analysis

  1. Rhodium-catalyzed direct ortho C-N bond formation of aromatic azo compounds with azides. (United States)

    Wang, Hao; Yu, Yang; Hong, Xiaohu; Tan, Qitao; Xu, Bin


    An efficient rhodium-catalyzed regioselective C-N bond formation of azo compounds in good to excellent yields through C-H bond functionalization using azides as the nitrogen source was developed. Alkyl, aryl, and sulfonyl azides could be efficiently assembled in this reaction with excellent functional group tolerance.

  2. Stoichiometric and Catalytic Synthesis of Alkynylphosphines

    Directory of Open Access Journals (Sweden)

    Annie-Claude Gaumont


    Full Text Available Alkynylphosphines or their borane complexes are available either through C–P bond forming reactions or through modification of the phosphorus or the alkynyl function of various alkynyl phosphorus derivatives. The latter strategy, and in particular the one involving phosphoryl reduction by alanes or silanes, is the method of choice for preparing primary and secondary alkynylphosphines, while the former strategy is usually employed for the synthesis of tertiary alkynylphosphines or their borane complexes. The classical C–P bond forming methods rely on the reaction between halophosphines or their borane complexes with terminal acetylenes in the presence of a stoichiometric amount of organometallic bases, which precludes the access to alkynylphosphines bearing sensitive functional groups. In less than a decade, efficient catalytic procedures, mostly involving copper complexes and either an electrophilic or a nucleophilic phosphorus reagent, have emerged. By proceeding under mild conditions, these new methods have allowed a significant broadening of the substituent scope and structure complexity.

  3. Steam reformer with catalytic combustor (United States)

    Voecks, Gerald E. (Inventor)


    A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

  4. Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions. (United States)

    Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A


    step in designing Mn III -peroxo complexes that convert cleanly to high-valent Mn-oxo species. Although some synthetic Mn IV -oxo complexes show great potential for oxidizing substrates with strong C-H bonds, most Mn IV -oxo species are sluggish oxidants. Both two-state reactivity and thermodynamic arguments have been put forth to explain these observations. To address these issues, we generated a series of Mn IV -oxo complexes supported by neutral, pentadentate ligands with systematically perturbed equatorial donation. Kinetic investigations of these complexes revealed a correlation between equatorial ligand-field strength and hydrogen-atom and oxygen-atom transfer reactivity. While this trend can be understood on the basis of the two-state reactivity model, the reactivity trend also correlates with variations in Mn III/IV reduction potential caused by changes in the ligand field. This work demonstrates the dramatic influence simple ligand perturbations can have on reactivity but also illustrates the difficulties in understanding the precise basis for a change in reactivity. In the enzyme manganese lipoxygenase, an active-site Mn III -hydroxo adduct initiates substrate oxidation by abstracting a hydrogen atom from a C-H bond. Precedent for this chemistry from synthetic Mn III -hydroxo centers is rare. To better understand hydrogen-atom transfer by Mn III centers, we developed a pair of Mn III -hydroxo complexes, formed in high yield from dioxygen oxidation of Mn II precursors, capable of attacking weak O-H and C-H bonds. Kinetic and computational studies show a delicate interplay between thermodynamic and steric influences in hydrogen-atom transfer reactivity, underscoring the potential of Mn III -hydroxo units as mild oxidants.


    African Journals Online (AJOL)

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    acetylchlorophosphonazo(CPApA) by hydrogen peroxide in 0.10 M phosphoric acid. A novel catalytic kinetic-spectrophotometric method is proposed for the determination of copper based on this principle. Copper(II) can be determined spectrophotometrically ...


    African Journals Online (AJOL)

    Based on the property that in 0.12 M sulfuric acid medium titanium(IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of titanium is

  7. Grieks aan die P.U. vir C.H.O.*

    Directory of Open Access Journals (Sweden)

    J.H. Grobler


    Full Text Available Met hierdie rede word betoog dat die patroon van die studie van Grieks wat deur die Atheners vier tot vyf eeue v.C. daargestel is en deur die Alexandryne en Pergamon van drie eeue v.C. tot drie eeu n.C. verder gevorm is, deur die eeue nagevolg is, telkens met die oogmerke wat gepas het by die bepaalde tye, tot in die twintigste eeu. Volgens hierdie patroon is Attiese Grieks bestudeer. Die Attiese Grieks is die literêre taal, die skryftaal, van Athene in die vyfde en vierde eeue v.C. Hierdie tradisie is ook aan die P.U. vir C.H.O. nagevolg. Aan hierdie Universiteit is die studente van Grieks hoofsaaklik, indien nie uitsluitlik nie, voornemende teologiese studente.

  8. R.E.A.C.H. to Teach: Making Patient and Family Education "Stick". (United States)

    Cutilli, Carolyn Crane


    Healthcare professionals teach patients and families about their health every day. Regulatory and accreditation organizations mandate patient and family education to promote better health outcomes. And recently, financial rewards for healthcare organizations are being tied to patient satisfaction (Hospital Consumer Assessment of Healthcare Providers and Systems-HCAHPS). A University of Pennsylvania Health System group of staff and patients, devoted to excellence in patient and family education, developed the graphic "R.E.A.C.H. to Teach." The purpose of the graphic is to make evidence-based practice (EBP) for patient and family education "stick" with staff. The group used concepts from the marketing book, Made to Stick, to demonstrate how to develop effective staff and patient and family education. Ideas (education) that survive ("stick") have the following attributes: simple, unexpected, concrete, credible, emotional, and narrative (story). This article demonstrates how to apply these principles and EBP to patient and family education.

  9. 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.

  10. 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.

  11. C.H. Dodd se verstaansraamwerk vir die Johannes-evangelie: ’n Evaluasie

    Directory of Open Access Journals (Sweden)

    Jan G. van der Watt


    Full Text Available C.H. Dodd’s framework for understanding the Gospel according to John: An evaluation. During the previous century Dodd was one of the most significant and influential interpreters of the Gospel of John. His views on the symbolic nature of the Gospel formed the basis of his hermeneutical program for understanding the Gospel. He understood the Johannine symbols in the light of what he regarded as the relevant background material. Theologically he interprets the symbols within a Platonic-like structure, arguing that the symbols in John function as hermeneutical bridges between the background material and the theological formation of the Gospel of John. In subsequent literary studies this approach was and still is questioned.

  12. Benchmark reaction rates, the stability of biological molecules in water, and the evolution of catalytic power in enzymes. (United States)

    Wolfenden, Richard


    The rates of enzyme reactions fall within a relatively narrow range. To estimate the rate enhancements produced by enzymes, and their expected affinities for transition state analog inhibitors, it is necessary to measure the rates of the corresponding reactions in water in the absence of a catalyst. This review describes the spontaneous cleavages of C-C, C-H, C-N, C-O, P-O, and S-O bonds in biological molecules, as well as the uncatalyzed reactions that correspond to phosphoryl transfer reactions catalyzed by kinases and to peptidyl transfer in the ribosome. The rates of these reactions, some with half-lives in excess of one million years, span an overall range of 10¹⁹-fold. Moreover, the slowest reactions tend to be most sensitive to temperature, with rates that increase as much as 10⁷-fold when the temperature is raised from 25° to 100°C. That tendency collapses, by many orders of magnitude, the time that would have been required for chemical evolution on a warm earth. If the catalytic effect of primitive enzymes, like that of modern enzymes and many nonenzymatic catalysts, were mainly to reduce a reaction's enthalpy of activation, then the resulting rate enhancement would have increased automatically as the surroundings cooled. By reducing the time required for early chemical evolution in a warm environment, these findings counter the view that not enough time has passed for terrestrial life to have evolved to its present level of complexity.

  13. Substrate-Triggered Formation and Remarkable Stability of the C-H-Cleaving Chloroferryl Intermediate in the Aliphatic Halogenase, SyrB2† (United States)

    Matthews, Megan L.; Krest, Courtney M.; Barr, Eric W.; Vaillancourt, Frédéric H.; Walsh, Christopher T.; Green, Michael T.; Krebs, Carsten; Bollinger, J. Martin


    Aliphatic halogenases activate O2, cleave α-ketoglutarate (αKG) to CO2 and succinate, and form haloferryl [X-Fe(IV)=O; X = Cl, Br] complexes that cleave aliphatic C-H bonds to install halogens during the biosynthesis of natural products by non-ribosomal peptide synthetases (NRPSs). For the related αKG-dependent dioxygenases, it has been shown that reaction of the Fe(II) cofactor with O2 to form the C-H-cleaving ferryl complex is “triggered” by binding of the target substrate. In this study, we have tested for and defined structural determinants of substrate triggering (ST) in the halogenase, SyrB2, from the syringomycin E biosynthetic NRPS of Pseudomonas syringae B301D. As for other halogen ases, the substrate of SyrB2 is complex, consisting of l-Thr tethered via thioester linkage to a covalently bound phosphopantetheine (PPant) cofactor of a carrier protein, SyrB1. Without an appended amino acid, SyrB1 does not trigger formation of the chloroferryl intermediate state in SyrB2, even in the presence of free l-Thr or its analogues, but SyrB1 charged either by l-Thr or by any of several non-native amino acids does trigger the reaction by as much as 8,000-fold (for l-Thr-S-SyrB1). Triggering efficacy is sensitive to the structures of both the amino acid and the carrier protein, being diminished by 5–20-fold when the native l-Thr is replaced by another amino acid and by ∼ 40-fold when SyrB1 is replaced by a heterologous carrier protein, CytC2. The directing effect of the carrier protein and consequent tolerance for profound modifications to the target amino acid allow the chloroferryl state to be formed in the presence of substrates that perturb the ratio of its two putative coordination isomers, lack the target C-H bond (l-Ala-S-SyrB1), or contain a C-H bond of enhanced strength (l-cyclopropylglycyl-S-SyrB1). For the latter two cases, the SyrB2 chloroferryl state so formed exhibits unprecedented stability (t1/2 = 30 – 110 min at 0 °C), can be trapped in

  14. Effects of metal elements in catalytic growth of carbon nanotubes/graphene: A first principles DFT study

    International Nuclear Information System (INIS)

    Li, Jingde; Croiset, Eric; Ricardez-Sandoval, Luis


    Graphical abstract: - Highlights: • Role of metals in the catalytic growth of CNTs or graphene was studied using DFT. • The results explain why Ni-based catalyst is suitable for growing CNTs. • Cu based alloys, e.g. Cu 8 Ni, are found appropriate catalyst for graphene synthesis. - Abstract: Role of metals in the catalytic Chemical Vapor Deposition (CVD) growth of carbon nanotubes (CNTs) or graphene was investigated using DFT. Crucial processes involved in the growth of CNTs/graphene: methane dissociation to produce C, C diffusion and nucleation kinetics were studied on the (1 1 1) surface of different transition metals, i.e., Fe, Co, Ni, and Cu. Based on the DFT calculation results, the present study explains why Ni-based catalyst is a suitable CVD substrate for growing CNTs: it has a moderate reactivity towards methane dissociation; low energy barrier for C atom surface diffusion, which makes C to diffuse easily to the metal/CNTs edges and contribute to CNTs growth; relatively high nucleation barriers, making it more resistant for deactivation caused by the cover of carbon clusters. Meanwhile, this study also shows that Cu may be an appropriate catalyst for graphene synthesis due to the particularly low diffusion and nucleation barriers of C atoms on Cu, which suggest that C atoms tend to be more uniformly distributed and nucleate easily on the Cu surface. Key limitation of Cu is the low reactivity of this metal towards methane dissociation. Since Fe and Ni are very reactive towards C-H bond breaking, Cu based alloys, e.g. Cu 8 Ni, were proposed as a suitable catalyst for graphene production

  15. Bipyridine- and phenanthroline-based metal-organic frameworks for highly efficient and tandem catalytic organic transformations via directed C-H activation

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal [Univ. of Chicago, Chicago, IL (United States); Zhang, Teng [Univ. of Chicago, Chicago, IL (United States); Greene, Francis X. [Univ. of Chicago, Chicago, IL (United States); Lin, Wenbin [Univ. of Chicago, Chicago, IL (United States)


    We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal–organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)]2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C–H borylation of arenes using B₂pin₂. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C–H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.

  16. Engineering Porous Polymer Hollow Fiber Microfluidic Reactors for Sustainable C-H Functionalization. (United States)

    He, Yingxin; Rezaei, Fateme; Kapila, Shubhender; Rownaghi, Ali A


    Highly hydrophilic and solvent-stable porous polyamide-imide (PAI) hollow fibers were created by cross-linking of bare PAI hollow fibers with 3-aminopropyl trimethoxysilane (APS). The APS-grafted PAI hollow fibers were then functionalized with salicylic aldehyde for binding catalytically active Pd(II) ions through a covalent postmodification method. The catalytic activity of the composite hollow fiber microfluidic reactors (Pd(II) immobilized APS-grafted PAI hollow fibers) was tested via heterogeneous Heck coupling reaction of aryl halides under both batch and continuous-flow reactions in polar aprotic solvents at high temperature (120 °C) and low operating pressure. X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) analyses of the starting and recycled composite hollow fibers indicated that the fibers contain very similar loadings of Pd(II), implying no degree of catalyst leaching from the hollow fibers during reaction. The composite hollow fiber microfluidic reactors showed long-term stability and strong control over the leaching of Pd species.

  17. Selective Hydrogen Atom Abstraction via Induced Bond Polarization: The Direct -Arylation of Alcohols via Photoredox, HAT and Nickel Catalysis. (United States)

    Twilton, Jack; Christensen, Melodie; DiRocco, Daniel A; Ruck, Rebecca T; Davies, Ian W; MacMillan, David William


    The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation protocol for the selective functionalization of alcohol -hydroxy C-H bonds. This approach employs zinc-mediated alcohol deprotonation to activate -hydroxy C-H bonds while simultaneously suppressing C-O bond formation by inhibiting formation of nickel alkoxide species. The use of Zn based Lewis acids also deactivates other hydridic bonds such as -amino and -oxy C-H bonds. This technology facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3-step synthesis of the Prozac exemplifies the utility of this new method. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Catalytic thermal barrier coatings (United States)

    Kulkarni, Anand A.; Campbell, Christian X.; Subramanian, Ramesh


    A catalyst element (30) for high temperature applications such as a gas turbine engine. The catalyst element includes a metal substrate such as a tube (32) having a layer of ceramic thermal barrier coating material (34) disposed on the substrate for thermally insulating the metal substrate from a high temperature fuel/air mixture. The ceramic thermal barrier coating material is formed of a crystal structure populated with base elements but with selected sites of the crystal structure being populated by substitute ions selected to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a higher rate than would the base compound without the ionic substitutions. Precious metal crystallites may be disposed within the crystal structure to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a lower light-off temperature than would the ceramic thermal barrier coating material without the precious metal crystallites.

  19. 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...

  20. Stereodivergent synthesis of arylcyclopropylamines by sequential C-H borylation and Suzuki-Miyaura coupling. (United States)

    Miyamura, Shin; Araki, Misaho; Suzuki, Takayoshi; Yamaguchi, Junichiro; Itami, Kenichiro


    A step-economical and stereodivergent synthesis of privileged 2-arylcyclopropylamines (ACPAs) through a C(sp(3))-H borylation and Suzuki-Miyaura coupling sequence has been developed. The iridium-catalyzed C-H borylation of N-cyclopropylpivalamide proceeds with cis selectivity. The subsequent B-cyclopropyl Suzuki-Miyaura coupling catalyzed by [PdCl2(dppf)]/Ag2O proceeds with retention of configuration at the carbon center bearing the Bpin group, while epimerization at the nitrogen-bound carbon atoms of both the starting materials and products is observed under the reaction conditions. This epimerization is, however, suppressed in the presence of O2. The present new ACPA synthesis results in not only a significant reduction in the steps required for making ACPA derivatives, but also the ability to access either isomer (cis or trans) by simply changing the atmosphere (N2 or O2) in the coupling stage. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Adsorption of alcohols and fatty acids onto hydrogenated (a-C:H) DLC coatings (United States)

    Simič, R.; Kalin, M.; Kovač, J.; Jakša, G.


    Information about the interactions between lubricants and DLC coatings is scarce, despite there having been many studies over the years. In this investigation we used ToF-SIMS, XPS and contact-angle analyses to examine the adsorption ability and mechanisms with respect to two oiliness additives, i.e., hexadecanol and hexadecanoic acid, on an a-C:H coating. In addition, we analyzed the resistance of the adsorbed films to external influences like solvent cleaning. The results show that both molecules adsorb onto surface oxides and hydroxides present on the initial DLC surface and shield these structures with their hydrocarbon tails. This makes the surfaces less polar, which is manifested in a smaller polar component of the surface energy. We also showed that ultrasonic cleaning in heptane has no significant effect on the quantity of adsorbed molecules or on their chemical state. This not only shows the relatively strong adsorption of these molecules, but also provides useful information for future experimental work. Of the two examined molecules, the acid showed a greater adsorption ability than the alcohol, which explains some of the previously reported better tribological properties in the case of the acid with respect to the alcohol.

  2. Influence of modulation periods on the tribological behavior of Si/a-C: H multilayer film (United States)

    Zhu, Linan; Wu, Yanxia; Zhang, Shujiao; Yu, Shengwang; Tang, Bin; Liu, Ying; Zhou, Bing; Shen, Yanyan


    A series of Si/a-C: H multilayer films with different modulation periods were fabricated on stainless steel and silicon substrates by radio-frequency magnetron sputtering. The influence of the modulation period on the structure, morphology, mechanical properties and tribological behaviors in different environments (air, simulated acid rain, and NaCl solution) was investigated. The results show that the content of the sp2 hybrid carbon, surface roughness and hardness of the multilayer film increased firstly and then decreased with the decreased modulation period. Furthermore, the combination of the sublayer agrees well with the formation of the SiC crystal at the interface. Interestingly, the films show quite substantially different tribological properties in various test environments. The lowest friction coefficient is 0.2 for the S1 film in air. However, the lowest friction coefficient can reach 0.13 in solution. Importantly, the tribological behavior of the multilayer film is mainly determined by its hardness, as well as surface roughness in air while it is closely related with modulation period and interface structure in solution.

  3. Ultraviolet laser deposition of graphene thin films without catalytic layers

    KAUST Repository

    Sarath Kumar, S. R.


    In this letter, the formation of nanostructured graphene by ultraviolet laser ablation of a highly ordered pyrolytic graphite target under optimized conditions is demonstrated, without a catalytic layer, and a model for the growth process is proposed. Previously, graphene film deposition by low-energy laser (2.3 eV) was explained by photo-thermal models, which implied that graphene films cannot be deposited by laser energies higher than the C-C bond energy in highly ordered pyrolytic graphite (3.7 eV). Here, we show that nanostructured graphene films can in fact be deposited using ultraviolet laser (5 eV) directly over different substrates, without a catalytic layer. The formation of graphene is explained by bond-breaking assisted by photoelectronic excitation leading to formation of carbon clusters at the target and annealing out of defects at the substrate.

  4. 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.

  5. Catalytic reduction of NO by methane using a Pt/C/polybenzimidazole/Pt/C fuel cell

    DEFF Research Database (Denmark)

    Petrushina, Irina; Cleemann, Lars Nilausen; Refshauge, Rasmus


    The catalytic NO reduction by methane was studied using a (NO,CH4,Ar),Pt|polybenzimidazole(PBI)–H3PO4|Pt,(H2,Ar) fuel cell at 135 and 165°C. It has been found that, without any reducing agent (like CH4), NO can be electrochemically reduced in the (NO, Ar), Pt/C|PBI–H3PO4|Pt/C, (H2,Ar) fuel cell...

  6. Catalytic gasification of automotive shredder residues with hydrogen generation (United States)

    Lin, Kuen-Song; Chowdhury, Sujan; Wang, Ze-Ping

    Hydrogen is a clean and new energy carrier to generate power through the Proton exchange membrane fuel cell (PEMFC) system. Hydrogen can be effectively turned out through the catalytic gasification of organic material such as automotive shredder residues (ASR). The main objective of this manuscript is to present an analysis of the catalytic gasification of ASR for the generation of high-purity hydrogen in a lab-scale fixed-bed downdraft gasifier using 15 wt.% NiO/Al 2O 3 catalysts at 760-900 K. In the catalytic gasification process, reduction of Ni(II) catalyst into Ni(0) has been confirmed through XANES spectra and consequently EXAFS data shows that the central Ni atoms have Ni-O and Ni-Ni bonds with bond distances of 2.03 ± 0.05 and 2.46 ± 0.05 Å, respectively. ASR is partially oxidized and ultimately converts into hydrogen rich syngas (CO and H 2) and increases of the reaction temperature are favored the generation of hydrogen with decomposition of the CO. As well, approximately 220 kg h -1 of ASR would be catalytically gasified at 760-900 K and 46.2 atm with the reactor volume 0.27 m 3 to obtain approximately 3.42 × 10 5 kcal h -1 of thermal energy during over 87% syngas generation with the generation of 100 kW electric powers.

  7. 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...

  8. 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.

  9. Characterization of the visible photoluminescence from porous a-Si:H and porous a-Si:C:H thin films

    Energy Technology Data Exchange (ETDEWEB)

    Estes, M.J. [Wright Lab., Wright-Patterson AFB, OH (United States). Avionics Directorate; Hirsch, L.R.; Wichart, S.; Moddel, G. [Univ. of Colorado, Boulder, CO (United States)


    The authors report on the influence of doping, temperature, porosity, and bandgap on the visible photoluminescence properties of anodically-etched porous a-Si:H and a-Si:C:H thin films. Only boron-doped, p-type a-Si:H or a-Si:C:H samples exhibited any visible photoluminescence. The authors see evidence of discrete defect or impurity levels in temperature-dependent luminescence measurements. Unlike in porous crystalline silicon, they see no correlation of luminescence energy with porosity. The authors do, though, observe a correlation of luminescence energy with bandgap of the starting a-Si:C:H films. They discuss the implication of these observations on the nature of the luminescence mechanism.

  10. Integrated catalytic and electrocatalytic conversion of substituted phenols and diaryl ethers

    Energy Technology Data Exchange (ETDEWEB)

    Song, Yang; Chia, Shao H.; Sanyal, Udishnu; Gutierrez, Oliver Y.; Lercher, Johannes A.


    Electrocatalytic hydrogenation and catalytic thermal hydrogenation of substituted phenols and diaryl ethers were studied on carbon-supported Rh. For electrocatalytic and catalytic thermal hydrogen addition reactions, the dominant reaction pathway is hydrogenation to cyclic alcohols and cycloalkyl ethers. The presence of substituting methyl or methoxy groups led to lower rates compared to unsubstituted phenol or diphenyl ether. Methoxy or benzyloxy groups, however, undergo C-O bond cleavage via hydrogenolysis and hydrolysis (minor pathway).

  11. P(O)R2-Directed Enantioselective C-H Olefination toward Chiral Atropoisomeric Phosphine-Olefin Compounds. (United States)

    Li, Shi-Xia; Ma, Yan-Na; Yang, Shang-Dong


    An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R 2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.

  12. Novel Catalytic Membrane Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stuart Nemser, PhD


    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  13. Transition-metal-catalyzed enantioselective heteroatom-hydrogen bond insertion reactions. (United States)

    Zhu, Shou-Fei; Zhou, Qi-Lin


    Carbon-heteroatom bonds (C-X) are ubiquitous and are among the most reactive components of organic compounds. Therefore investigations of the construction of C-X bonds are fundamental and vibrant fields in organic chemistry. Transition-metal-catalyzed heteroatom-hydrogen bond (X-H) insertions via a metal carbene or carbenoid intermediate represent one of the most efficient approaches to form C-X bonds. Because of the availability of substrates, neutral and mild reaction conditions, and high reactivity of these transformations, researchers have widely applied transition-metal-catalyzed X-H insertions in organic synthesis. Researchers have developed a variety of rhodium-catalyzed asymmetric C-H insertion reactions with high to excellent enantioselectivities for a wide range of substrates. However, at the time that we launched our research, very few highly enantioselective X-H insertions had been documented primarily because of a lack of efficient chiral catalysts and indistinct insertion mechanisms. In this Account, we describe our recent studies of copper- and iron-catalyzed asymmetric X-H insertion reactions by using chiral spiro-bisoxazoline and diimine ligands. The copper complexes of chiral spiro-bisoxazoline ligands proved to be highly enantioselective catalysts for N-H insertions of α-diazoesters into anilines, O-H insertions of α-diazoesters into phenols and water, O-H insertions of α-diazophosphonates into alcohols, and S-H insertions of α-diazoesters into mercaptans. The iron complexes of chiral spiro-bisoxazoline ligands afforded the O-H insertion of α-diazoesters into alcohols and water with unprecedented enantioselectivities. The copper complexes of chiral spiro-diimine ligands exhibited excellent reactivity and enantioselectivity in the Si-H insertion of α-diazoacetates into a wide range of silanes. These transition-metal-catalyzed X-H insertions have many potential applications in organic synthesis because the insertion products, including chiral

  14. Computational Modeling of the Catalytic Cycle of Glutathione Peroxidase Nanomimic. (United States)

    Kheirabadi, Ramesh; Izadyar, Mohammad


    To elucidate the role of a derivative of ebselen as a mimic of the antioxidant selenoenzyme glutathione peroxidase, density functional theory and solvent-assisted proton exchange (SAPE) were applied to model the reaction mechanism in a catalytic cycle. This mimic plays the role of glutathione peroxidase through a four-step catalytic cycle. The first step is described as the oxidation of 1 in the presence of hydrogen peroxide, while selenoxide is reduced by methanthiol at the second step. In the third step of the reaction, the reduction of selenenylsulfide occurs by methanthiol, and the selenenic acid is dehydrated at the final step. Based on the kinetic parameters, step 4 is the rate-determining step (RDS) of the reaction. The bond strength of the atoms involved in the RDS is discussed with the quantum theory of atoms in molecules (QTAIM). Low value of electron density, ρ(r), and positive Laplacian values are the evidence for the covalent nature of the hydrogen bonds rupture (O 30 -H 31 , O 33 -H 34 ). A change in the sign of the Laplacian, L(r), from the positive value in the reactant to a negative character at the transition state indicates the depletion of the charge density, confirming the N 5 -H 10 and O 11 -Se 1 bond breaking. The analysis of electron location function (ELF) and localized orbital locator (LOL) of the Se 1 -N 5 and Se 1 -O 11 bonds have been done by multi-WFN program. High values of ELF and LOL at the transition state regions between the Se, N, and O atoms display the bond formation. Finally, the main donor-acceptor interaction energies were analyzed using the natural bond orbital analysis for investigation of their stabilization effects on the critical bonds at the RDS.

  15. X hydrogen bonds

    Indian Academy of Sciences (India)

    sigma electrons, can be hydrogen bond acceptors.11–14. The recent IUPAC report and recommendation on hydro gen bond have recognised the diverse nature of hydro- gen bond donors and acceptors.13,14. Unlike methane, hydrogen bonding by higher alkanes has not received much attention. One of the earlier works.

  16. Adhesive wafer bonding (United States)

    Niklaus, F.; Stemme, G.; Lu, J.-Q.; Gutmann, R. J.


    Wafer bonding with intermediate polymer adhesives is an important fabrication technique for advanced microelectronic and microelectromechanical systems, such as three-dimensional integrated circuits, advanced packaging, and microfluidics. In adhesive wafer bonding, the polymer adhesive bears the forces involved to hold the surfaces together. The main advantages of adhesive wafer bonding include the insensitivity to surface topography, the low bonding temperatures, the compatibility with standard integrated circuit wafer processing, and the ability to join different types of wafers. Compared to alternative wafer bonding techniques, adhesive wafer bonding is simple, robust, and low cost. This article reviews the state-of-the-art polymer adhesive wafer bonding technologies, materials, and applications.

  17. Glass-aluminium bonded joints ; testing, comparing and designing for the ATP

    NARCIS (Netherlands)

    Richemont, S.A.J. de; Veer, F.A.


    This article presents the research to the bonded joints of the All Transparent Pavilion (ATP), an experimental project built in November 2004 at the faculty of Architecture in Delft. The pavilion is designed to use structural glass elements, bonded with Delo Photobond GB 368, a photo-catalytic

  18. Palladium-Catalyzed Enantioselective C-H Activation of Aliphatic Amines Using Chiral Anionic BINOL-Phosphoric Acid Ligands. (United States)

    Smalley, Adam P; Cuthbertson, James D; Gaunt, Matthew J


    The design of an enantioselective Pd(II)-catalyzed C-H amination reaction is described. The use of a chiral BINOL phosphoric acid ligand enables the conversion of readily available amines into synthetically valuable aziridines in high enantiomeric ratios. The aziridines can be derivatized to afford a range of chiral amine building blocks incorporating motifs readily encountered in pharmaceutically relevant molecules.

  19. A selective C-H insertion/olefination protocol for the synthesis of α-methylene-γ-butyrolactone natural products. (United States)

    Lloyd, Matthew G; D'Acunto, Mariantonietta; Taylor, Richard J K; Unsworth, William P


    A regio- and stereoselective one-pot C-H insertion/olefination protocol has been developed for the late stage installation of α-methylene-γ-butyrolactones into conformationally restricted cyclohexanol-derivatives. The method has been successfully applied in the total synthesis of eudesmanolide natural product frameworks, including α-cyclocostunolide.

  20. Palladium-Catalyzed C-H Functionalization Using Guanidine as a Directing Group: Ortho Arylation and Olefination of Arylguanidines (United States)

    Shao, Jiaan; Chen, Wenteng; Giulianotti, Marc A.; Houghten, Richard A.; Yu, Yongping


    Palladium-catalyzed C-H functionalization using guanidine as the directing group was achieved under mild reaction conditions. Various guanidine derivatives were produced in moderate to good yields by using simple unactivated arenes or ethyl acrylate as the source of arylation or olefination respectively. PMID:23095022

  1. Palladium-catalyzed C-H olefination of uracils and caffeines using molecular oxygen as the sole oxidant. (United States)

    Zhang, Xinyu; Su, Lv; Qiu, Lin; Fan, Zhenwei; Zhang, Xiaofeng; Lin, Shen; Huang, Qiufeng


    The palladium-catalyzed oxidative C-H olefination of uracils or caffeines with alkenes using an atmospheric pressure of molecular oxygen as the sole oxidant has been disclosed. This novel strategy offers an efficient and environmentally friendly method to biologically important C5-alkene uracil derivatives or C8-alkene caffeine derivatives.

  2. 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.

  3. C5-Regioselective C-H fluorination of 8-aminoquinoline amides and sulfonamides with Selectfluor under metal-free conditions. (United States)

    Zhang, Yingchao; Wen, Chunxia; Li, Jizhen


    A novel and efficient regioselective C-H fluorination of 8-aminoquinoline amides and sulfonamides at the C5 position was achieved. Using Selectfluor as a "F" reagent and HOAc as an additive, the reaction proceeds smoothly via a radical pathway. This method features metal-free conditions, a broad substrate scope and operational simplicity.

  4. Rhodium-Catalyzed Direct Ortho C-H Arylation Using Ketone as Directing Group with Boron Reagent. (United States)

    Zhang, Bing; Wang, Huai-Wei; Kang, Yan-Shang; Zhang, Ping; Xu, Hua-Jin; Lu, Yi; Sun, Wei-Yin


    A general method for selective ortho C-H arylation of ketone, with boron reagent enabled by rhodium complexes with excellent yields, is developed. The transformation is characterized by the use of air-stable Rh catalyst, high monoarylation selectivity, and excellent yields of most of the substrates.

  5. Catalytic Antibodies: Concept and Promise

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 12; Issue 11. Catalytic Antibodies: Concept and Promise. Desirazu N Rao Bharath Wootla. General Article Volume 12 Issue ... Keywords. Catalytic antibodies; abzymes; hybridome technology; Diels– Alder reaction; Michaelis– Menten kinetics; Factor VIII.

  6. 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)

  7. 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.)

  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. 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 [LFe 3 (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 Fe 3 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. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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.

    Pyrrole- and indole-fused isocoumarins constitute important structural units in natural products and pharmacophores, although the direct and selective bifunctionalization of pyrrole and indole remain a challenge. Herein, we report a one...

  11. Ru(II)-Catalyzed Oxidative Heck-Type Olefination of Aromatic Carboxylic Acids with Styrenes through Carboxylate-Assisted C-H Bond Activation. (United States)

    Dana, Suman; Mandal, Anup; Sahoo, Harekrishna; Mallik, Sumitava; Grandhi, Gowri Sankar; Baidya, Mahiuddin


    A straightforward synthesis of 2-styrylbenzoic acids from aryl carboxylic acids is disclosed through a carboxylate-assisted coupling under Ru(II) catalysis. This protocol is simple and exhibits broad scope with high tolerance of common organic functional groups, providing good to excellent yields of diverse olefinated products. The efficacy of this protocol has been showcased through sequential syntheses of isochromanone, isocoumarin, and formal synthesis of anacardic acid derivative in good yields.

  12. Magnetism, chemical bonding and hyperfine properties in the nanoscale antiferromagnet [Fe(O Me)2(O2 C C H2 Cl)]10

    International Nuclear Information System (INIS)

    Zeng, Z.; Duan, Y.; Guenzburger, Diana


    The electronic and magnetic properties of the nanometer-size antiferromagnet (the ferric wheel molecule) are investigated with the first-principles spin-polarized Discrete Variational Method, in the framework of Density Functional theory. Magnetic moments, densities of the states and charge and spin-density maps are obtained. The Moessbauer hyperfine parameters Isomer shift, Quadrupole Splitting and Hyperfine Field are obtained from the calculations and compared to reported experimental values when available. (author). 33 refs., 8 figs., 4 tabs

  13. Catalytic interface erosion

    International Nuclear Information System (INIS)

    Meng, H.; Cohen, E.G.D.


    We study interface erosion processes: catalytic erosions. We present two cases. (1) The erosion of a completely occupied lattice by one single moving particle starting from somewhere inside the lattice, considering deterministic as well as probabilistic erosion rules. In the latter case, the eroded regions appear to have interfaces with continuously tunable fractal dimensions. (2) The kinetic roughening of an initially flat surface, where ballistic or diffusion-limited particles, which remain intact themselves, erode the surface coming from the outside, using the same erosion rules as in (1). Many features resembling realistic interfaces, for example, islands and inlets, are generated. The dependence of the surface width on the system size is due to both the erosion mechanism and the way particles move before reaching the surface

  14. Catalytic detritiation of water

    International Nuclear Information System (INIS)

    Rogers, M.L.; Lamberger, P.H.; Ellis, R.E.; Mills, T.K.


    A pilot-scale system has been used at Mound Laboratory to investigate the catalytic detritiation of water. A hydrophobic, precious metal catalyst is used to promote the exchange of tritium between liquid water and gaseous hydrogen at 60 0 C. Two columns are used, each 7.5 m long by 2.5 cm ID and packed with catalyst. Water flow is 5-10 cm 3 /min and countercurrent hydrogen flow is 9,000-12,000 cm 3 /min. The equipment, except for the columns, is housed in an inert atmosphere glovebox and is computer controlled. The hydrogen is obtained by electrolysis of a portion of the water stream. Enriched gaseous tritium is withdrawn for further enrichment. A description of the system is included along with an outline of its operation. Recent experimental data are discussed

  15. 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.

  16. Total synthesis of eudesmane terpenes by site-selective C-H oxidations. (United States)

    Chen, Ke; Baran, Phil S


    From menthol to cholesterol to Taxol, terpenes are a ubiquitous group of molecules (over 55,000 members isolated so far) that have long provided humans with flavours, fragrances, hormones, medicines and even commercial products such as rubber. Although they possess a seemingly endless variety of architectural complexities, the biosynthesis of terpenes often occurs in a unified fashion as a 'two-phase' process. In the first phase (the cyclase phase), simple linear hydrocarbon phosphate building blocks are stitched together by means of 'prenyl coupling', followed by enzymatically controlled molecular cyclizations and rearrangements. In the second phase (the oxidase phase), oxidation of alkenes and carbon-hydrogen bonds results in a large array of structural diversity. Although organic chemists have made great progress in developing the logic needed for the cyclase phase of terpene synthesis, particularly in the area of polyene cyclizations, much remains to be learned if the oxidase phase is to be mimicked in the laboratory. Here we show how the logic of terpene biosynthesis has inspired the highly efficient and stereocontrolled syntheses of five oxidized members of the eudesmane family of terpenes in a modicum of steps by a series of simple carbocycle-forming reactions followed by multiple site-selective inter- and intramolecular carbon-hydrogen oxidations. This work establishes an intellectual framework in which to conceive the laboratory synthesis of other complex terpenes using a 'two-phase' approach.

  17. Theoretical study of the C-H/O-H stretching vibrations in malonaldehyde (United States)

    Pitsevich, G. A.; Malevich, A. E.; Kozlovskaya, E. N.; Doroshenko, I. Yu.; Pogorelov, V. E.; Sablinskas, V.; Balevicius, V.


    IR and Raman spectra of the malonaldehyde molecule and its deuterated analogues were calculated in the B3LYP/cc-pVQZ approximation. Anharmonicity effects were taken into account both in the context of a standard model of the second order perturbation theory and by constructing the potential energy surfaces (PES) with a limited number of dimensions using the Cartesian coordinates of the hydroxyl hydrogen atom and the stretching coordinates of С-Н, C-D, O-H, and O-D bonds. It was shown that in each of the two equivalent forms of the molecule, besides the global minimum, an additional local minimum at the PES is formed with the energy more than 3000 cm-1 higher than the energy in the global minimum. Calculations carried out by constructing the 2D and 3D PESs indicate a high anharmonicity level and multiple manifestations of the stretching О-Н vibrations, despite the fact that the model used does not take into account the splitting of the ground-state and excited vibrational energy levels. In particular, the vibration with the frequency 3258 cm-1 may be associated with proton transfer to the region of a local minimum of energy. Comparing the results obtained with the experimental data presented in the literature allowed us to propose a new variant of bands assignments in IR and Raman spectra of the molecule in the spectral region 2500-3500 cm-1.

  18. Combined UV-C/H2O2-VUV processes for the treatment of an actual slaughterhouse wastewater. (United States)

    Naderi, Kambiz Vaezzadeh; Bustillo-Lecompte, Ciro Fernando; Mehrvar, Mehrab; Abdekhodaie, Mohammad Jafar


    In this study, a three-factor, three-level Box-Behnken design with response surface methodology were used to maximize the TOC removal and minimize the H 2 O 2 residual in the effluent of the combined UV-C/H 2 O 2 -VUV system for the treatment of an actual slaughterhouse wastewater (SWW) collected from one of the meat processing plants in Ontario, Canada. The irradiation time and the initial concentrations of total organic carbon (TOC o ) and hydrogen peroxide (H 2 O 2o ) were the three predictors, as independent variables, studied in the design of experiments. The multiple response approach was used to obtain desirability response surfaces at the optimum factor settings. Subsequently, the optimum conditions to achieve the maximum percentage TOC removal of 46.19% and minimum H 2 O 2 residual of 1.05% were TOC o of 213 mg L -1 , H 2 O 2o of 450 mg L -1 , and irradiation time of 9 min. The attained optimal operating conditions were validated with a complementary test. Consequently, the TOC removal of 45.68% and H 2 O 2 residual of 1.03% were achieved experimentally, confirming the statistical model reliability. Three individual processes, VUV alone, VUV/H 2 O 2 , and UV-C/H 2 O 2 , were also evaluated to compare their performance for the treatment of the actual SWW using the optimum parameters obtained in combined UV-C/H 2 O 2 -VUV processes. Results confirmed that an adequate combination of the UV-C/H 2 O 2 -VUV processes is essential for an optimized TOC removal and H 2 O 2 residual. Finally, respirometry analyses were also performed to evaluate the biodegradability of the SWW and the BOD removal efficiency of the combined UV-C/H 2 O 2 -VUV processes.

  19. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik


    This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

  20. Catalytic activity of nuclease P1: Experiment and theory

    International Nuclear Information System (INIS)

    Miller, J.H.; Falcone, J.M.; Shibata, M.; Box, H.C.


    Nuclease P1 from Penicillium citrinum is a zinc dependent glyco-enzyme that recognizes single stranded DNA and RNA as substrates and hydrolyzes the phosphate ester bond. Nuclease Pl seems to recognize particular conformations of the phosphodiester backbone and shows significant variation in the rate of hydrolytic activity depending upon which nucleosides are coupled by the phosphodiester bond. The efficiency of nuclease Pl in hydrolyzing the phosphodiester bonds of a substrate can be altered by modifications to one of the substrate bases induced by ionizing radiation or oxidative stress. Measurements have been made of the effect of several radiation induced lesions on the catalytic rate of nuclease Pl. A model of the structure of the enzyme has been constructed in order to better understand the binding and activity of this enzyme on various ssDNA substrates

  1. Dynamical Response of Catalytic Systems in a CS Corrected Environmental Transmission Electron Microscope

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; Dunin-Borkowski, Rafal E.; Boothroyd, Chris


    . In a catalytic reactor, the particles tend to sinter under reaction conditions resulting in the formation of larger particles and a loss of catalytic activity. Several models of sintering in different systems have been put forward [4,5]. However, most investigations have been post mortem studies, revealing only...... energies and energy barriers for sintering processes can be studied. The surface structures of catalytic materials are highly dependent on the surrounding atmosphere. The combined capabilities of ETEM and image CS correction provide unique possibilities to study this relationship. However, in order...... as function of Ar pressure in the pole piece gap. References [1] I. Chorkendorff and J.W. Niemantsverdriet, Concepts of Modern Catalysis and Kinetics, Wiley-VCH, Weinheim, 2003. [2] [3] A.K. Datye, J. Catal. 216 (2003) 144. [4] J.T. Richardson and J.G. Crump, J. Catal. 56 (1979) 417. [5] C. H...

  2. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.


    The focus of this thesis is the catalytic production of diesel from biomass, especially emphasising catalytic conversion of waste vegetable oils and fats. In chapter 1 an introduction to biofuels and a review on different catalytic methods for diesel production from biomass is given. Two of these methods have been used industrially for a number of years already, namely the transesterification (and esterification) of oils and fats with methanol to form fatty acid methyl esters (FAME), and the hydrodeoxygenation (HDO) of fats and oils to form straight-chain alkanes. Other possible routes to diesel include upgrading and deoxygenation of pyrolysis oils or aqueous sludge wastes, condensations and reductions of sugars in aqueous phase (aqueous-phase reforming, APR) for monofunctional hydrocarbons, and gasification of any type of biomass followed by Fischer-Tropsch-synthesis for alkane biofuels. These methods have not yet been industrialised, but may be more promising due to the larger abundance of their potential feedstocks, especially waste feedstocks. Chapter 2 deals with formation of FAME from waste fats and oils. A range of acidic catalysts were tested in a model fat mixture of methanol, lauric acid and trioctanoin. Sulphonic acid-functionalised ionic liquids showed extremely fast convertion of lauric acid to methyl laurate, and trioctanoate was converted to methyl octanoate within 24 h. A catalyst based on a sulphonated carbon-matrix made by pyrolysing (or carbonising) carbohydrates, so-called sulphonated pyrolysed sucrose (SPS), was optimised further. No systematic dependency on pyrolysis and sulphonation conditions could be obtained, however, with respect to esterification activity, but high activity was obtained in the model fat mixture. SPS impregnated on opel-cell Al{sub 2}O{sub 3} and microporous SiO{sub 2} (ISPS) was much less active in the esterification than the original SPS powder due to low loading and thereby low number of strongly acidic sites on the

  3. 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...

  4. Neutron diffraction study of phase relationship of Ti-C-H system

    International Nuclear Information System (INIS)

    Khidirov, I.; Mukhtarova, N.N.; Mirzaev, B.B.; Serikbaev, B.T.; Zaginaichenko, S.Yu.; Schur, D.V.; Pishuk, V.K.; Kuzmenko, L.V.; Garbuz, V.V.; Nuzhda, S.V.; Pishuk, O.V.


    temperature the sintering process is very active. Later on, the step increasing of temperature was carried out till 1000 deg. C with a step of 100 deg. C. The briquettes were exposed during 24 h at each temperature. With increasing temperature up to 800-1000 deg. C the pressured powder became well sintered and hydrogen emission from the sample was prevented. The final product was prepared after the annealing at 1000 deg. C followed by quenching in water. Compound of the samples was controlled by chemical analysis and compound of the single-phase samples also was controlled by minimizing the divergence factors of structure determination using neutron diffraction patterns. It is established that at hardening from 1000 deg. C in the samples with low concentration of C and H the solid solution of C and H in BCC β-Ti (with impurity of FCC- TiC x H y -phase) is formed. This metastable phase is stable enough at the room temperature. It is shown that at carbon concentration of 0.30 ≤ x ≤ 0.50 and y ≥ x in Ti-C-H system the ordered hexagonal close-packed (HCP) structure is stabilized, and at y x H y compounds have the ordered HCP structure corresponding to formula Ti 2 C 1-z H 2-z . The crystal structure of the phase is described within the framework of space group, where metal atoms are strongly displaced along c axis (Z Me =0.234±0.001) with respect to their ideal positions (z id =1/4). Step annealing of the single-phase solid solutions at temperatures of 700-600-500 deg. C during 24 h leads to decay of the samples, having concentration C/Ti≤0.43, the hydride phases being separated. Hence, the ordered solid solution Ti 2 C 1-x H 2-y is stable at concentrations 1.00≥C/Ti>0.43 (near carbon stoichiometry Ti 2 C), but it is metastable at concentrations 0.30≤C/T≤0.43. Compound TiC x H y at concentrations 0.45≤x≤0.55 and y< x can have both disordered (sp. gr. Fm3m) and ordered FCC-structure (sp. gr. Fd3m) depending on temperature. At temperatures lower than 600 deg. C

  5. Catalytic cracking with deasphalted oil

    Energy Technology Data Exchange (ETDEWEB)

    Beaton, W.I.; Taylor, J.L.; Peck, L.B.; Mosby, J.F.


    This patent describes a catalytic cracking process. It comprises: hydrotreating resid; thereafter deasphalting the hydrotreated resid to produce substantially deasphalted oil; catalytically cracking the hydrotreated oil in a catalytic cracking unit in the presence of a cracking catalyst to produce upgraded oil leaving coked catalyst; and regenerating the coked catalyst in the presence of a combustion-supporting gas comprising excess molecular oxygen in an amount greater than the stoichiometric amount required for substantially completely combusting the coke on the catalyst to carbon dioxide.

  6. Australia's Bond Home Bias


    Anil V. Mishra; Umaru B. Conteh


    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  7. Catalytic Membrane Sensors

    Energy Technology Data Exchange (ETDEWEB)

    Boyle, T.J.; Brinker, C.J.; Gardner, T.J.; Hughes, R.C.; Sault, A.G.


    The proposed "catalytic membrane sensor" (CMS) was developed to generate a device which would selectively identify a specific reagent in a complex mixture of gases. This was to be accomplished by modifying an existing Hz sensor with a series of thin films. Through selectively sieving the desired component from a complex mixture and identifying it by decomposing it into Hz (and other by-products), a Hz sensor could then be used to detect the presence of the select component. The proposed "sandwich-type" modifications involved the deposition of a catalyst layered between two size selective sol-gel layers on a Pd/Ni resistive Hz sensor. The role of the catalyst was to convert organic materials to Hz and organic by-products. The role of the membraneo was to impart both chemical specificity by molecukir sieving of the analyte and converted product streams, as well as controlling access to the underlying Pd/Ni sensor. Ultimately, an array of these CMS elements encompassing different catalysts and membranes were to be developed which would enable improved selectivity and specificity from a compiex mixture of organic gases via pattern recognition methodologies. We have successfully generated a CMS device by a series of spin-coat deposited methods; however, it was determined that the high temperature required to activate the catalyst, destroys the sensor.

  8. Catalytic cracking of lignites

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, M.; Nowak, S.; Naegler, T.; Zimmermann, J. [Hochschule Merseburg (Germany); Welscher, J.; Schwieger, W. [Erlangen-Nuernberg Univ. (Germany); Hahn, T. [Halle-Wittenberg Univ., Halle (Germany)


    A most important factor for the chemical industry is the availability of cheap raw materials. As the oil price of crude oil is rising alternative feedstocks like coal are coming into focus. This work, the catalytic cracking of lignite is part of the alliance ibi (innovative Braunkohlenintegration) to use lignite as a raw material to produce chemicals. With this new one step process without an input of external hydrogen, mostly propylene, butenes and aromatics and char are formed. The product yield depends on manifold process parameters. The use of acid catalysts (zeolites like MFI) shows the highest amount of the desired products. Hydrogen rich lignites with a molar H/C ratio of > 1 are to be favoured. Due to primary cracking and secondary reactions the ratio between catalyst and lignite, temperature and residence time are the most important parameter to control the product distribution. Experiments at 500 C in a discontinuous rotary kiln reactor show yields up to 32 wt-% of hydrocarbons per lignite (maf - moisture and ash free) and 43 wt-% char, which can be gasified. Particularly, the yields of propylene and butenes as main products can be enhanced four times to about 8 wt-% by the use of catalysts while the tar yield decreases. In order to develop this innovative process catalyst systems fixed on beads were developed for an easy separation and regeneration of the used catalyst from the formed char. (orig.)

  9. Rhodium-catalyzed direct C-H amination of benzamides with aryl azides: a synthetic route to diarylamines. (United States)

    Ryu, Jaeyune; Shin, Kwangmin; Park, Sae Hume; Kim, Ji Young; Chang, Sukbok


    No muss, no fuss: A rhodium-catalyzed direct intermolecular C-H amination of benzamides and ketoximes using aryl azides as the amine source has been developed. The reaction exhibits a broad substrate scope with excellent functional-group tolerance, requires no external oxidants, releases N(2) as the only by-product, and produces diarylamines in high yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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.

  11. C-H...pi interactions in the low-temperature crystal structures of alpha,omega-unsaturated linear hydrocarbons. (United States)

    Bond, Andrew D


    The low-temperature crystal structures of 1,7-octadiene (C8H14), 1,9-decadiene (C10H18), 1,7-octadiyne (C8H10) and 1,9-decadiyne (C10H14), determined following in situ crystal growth from the liquid, reveal the role of C-H...pi interactions in alpha,omega-unsaturated linear hydrocarbons in the solid state.

  12. Rh(III) -Catalyzed C-H Olefination of Benzoic Acids under Mild Conditions using Oxygen as the Sole Oxidant. (United States)

    Jiang, Quandi; Zhu, Changlei; Zhao, Huaiqing; Su, Weiping


    Phthalide skeletons have been synthesized for the first time through a Rh(III) -catalyzed C-H olefination of benzoic acids under mild conditions using oxygen as the sole oxidant. Aromatic acids bearing a variety of functional groups could react with diverse alkenes to afford the desired cyclized lactones or uncyclized alkenylarenes in moderate-to-excellent yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Remote meta-C-H olefination of phenylacetic acids directed by a versatile U-shaped template. (United States)

    Deng, Youqian; Yu, Jin-Quan


    meta-C-H olefination of phenylacetic acid derivatives has been achieved using a commercially available nitrile-containing template. The identification of N-formyl-protected glycine as the ligand (Formyl-Gly-OH) was crucial for the development of this reaction. Versatility of the template approach in accommodating macrocyclopalladation processes with different ring sizes is demonstrated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. 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")

  15. 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.

  16. 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

  17. Catalytic pyrolysis of lignocellulosic biomass

    NARCIS (Netherlands)

    Seshan, Kulathuiyer; Sa, Jacinto


    This chapter reports on the latest developments of biomass catalytic pyrolysis for the production of fuels. The primary focus is on the role of catalysts in the process, namely, their influence in the liquefaction of lignocellulosic biomass.

  18. Catalytic Mechanisms and Biocatalytic Applications of Aspartate and Methylaspartate Ammonia Lyases

    NARCIS (Netherlands)

    de Villiers, Marianne; Veetil, Vinod Puthan; Raj, Hans; de Villiers, Jandre; Poelarends, Gerrit J.


    Ammonia lyases catalyze the formation of alpha-beta-unsaturated bonds by the elimination of ammonia from their substrates. This conceptually straightforward reaction has been the emphasis of many studies, with the main focus on the catalytic mechanism of these enzymes and/or the use of these enzymes

  19. A Dynamic Supramolecular System Exhibiting Substrate Selectivity in the Catalytic Epoxidation of Olefins

    DEFF Research Database (Denmark)

    Jonsson, Stefan; Odille, Fabrice G. J.; Norrby, Per-Ola


    A dynamic supramolecular system involving hydrogen bonding between a Mn(III) salen catalyst and a Zn(II) porphyrin receptor exhibits selectivity for pyridine appended cis-beta-substituted styrene derivatives over phenyl appended derivatives in a catalytic epoxidation reaction....

  20. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand


    Modification of lignin is recognized as an important aspect of the successful refining of lignocellulosic biomass, and enzyme-assisted processing and upcycling of lignin is receiving significant attention in the literature. Laccases (EC 1.103.2) are taking the centerstage of this attention, since...... these enzymes may help degrading lignin, using oxygen as the oxidant. Laccases can catalyze polymerization of lignin, but the question is whether and how laccases can directly catalyze modification of lignin via catalytic bond cleavage. Via a thorough review of the available literature and detailed...... illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin...


    Directory of Open Access Journals (Sweden)

    J.E. de MEDEIROS


    Full Text Available The bond-order conservation method was used to study the catalytic decomposition of N2H4. Variation in the activation energy, E, of the most relevant steps was calculated as a function of the enthalpy of adsorption of N, QN, between 0 and 1250 kJmol-1. Results suggest that below QN = 520 kJmol-1 the catalytic decomposition of N2H4 produces mostly N2 and H2. Above QN = 520 kJmol-1, NH3 and N2 are the main products. Near QN = 520 kJmol-1 N2, H2 and NH3 are obtained, in agreement with experimental results on different metals.

  2. How absorbed hydrogen affects the catalytic activity of transition metals. (United States)

    Aleksandrov, Hristiyan A; Kozlov, Sergey M; Schauermann, Swetlana; Vayssilov, Georgi N; Neyman, Konstantin M


    Heterogeneous catalysis is commonly governed by surface active sites. Yet, areas just below the surface can also influence catalytic activity, for instance, when fragmentation products of catalytic feeds penetrate into catalysts. In particular, H absorbed below the surface is required for certain hydrogenation reactions on metals. Herein, we show that a sufficient concentration of subsurface hydrogen, H(sub) , may either significantly increase or decrease the bond energy and the reactivity of the adsorbed hydrogen, H(ad) , depending on the metal. We predict a representative reaction, ethyl hydrogenation, to speed up on Pd and Pt, but to slow down on Ni and Rh in the presence of H(sub) , especially on metal nanoparticles. The identified effects of subsurface H on surface reactivity are indispensable for an atomistic understanding of hydrogenation processes on transition metals and interactions of hydrogen with metals in general. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Chemoenzymatic Total Synthesis and Structural Diversification of Tylactone-Based Macrolide Antibiotics through Late-Stage Polyketide Assembly, Tailoring, and C-H Functionalization. (United States)

    Lowell, Andrew N; DeMars, Matthew D; Slocum, Samuel T; Yu, Fengan; Anand, Krithika; Chemler, Joseph A; Korakavi, Nisha; Priessnitz, Jennifer K; Park, Sung Ryeol; Koch, Aaron A; Schultz, Pamela J; Sherman, David H


    Polyketide synthases (PKSs) represent a powerful catalytic platform capable of effecting multiple carbon-carbon bond forming reactions and oxidation state adjustments. We explored the functionality of two terminal PKS modules that produce the 16-membered tylosin macrocycle, using them as biocatalysts in the chemoenzymatic synthesis of tylactone and its subsequent elaboration to complete the first total synthesis of the juvenimicin, M-4365, and rosamicin classes of macrolide antibiotics via late-stage diversification. Synthetic chemistry was employed to generate the tylactone hexaketide chain elongation intermediate that was accepted by the juvenimicin (Juv) ketosynthase of the penultimate JuvEIV PKS module. The hexaketide is processed through two complete modules (JuvEIV and JuvEV) in vitro, which catalyze elongation and functionalization of two ketide units followed by cyclization of the resulting octaketide into tylactone. After macrolactonization, a combination of in vivo glycosylation, selective in vitro cytochrome P450-mediated oxidation, and chemical oxidation was used to complete the scalable construction of a series of macrolide natural products in as few as 15 linear steps (21 total) with an overall yield of 4.6%.

  4. myo-Inositol Oxygenase: a Radical New Pathway for O2 and C-H Activation at a Nonheme Diiron Cluster (United States)

    Bollinger, J. Martin; Diao, Yinghui; Matthews, Megan L.; Xing, Gang; Krebs, Carsten


    The enzyme myo-inositol oxygenase (MIOX) catalyzes conversion of myo-inositol (cyclohexan-1,2,3,5/4,6-hexa-ol or MI) to D-glucuronate (DG), initiating the only known pathway in humans for catabolism of the carbon skeleton of cell-signaling inositol (poly)phosphates and phosphoinositides. Recent kinetic, spectroscopic, and crystallographic studies have shown that the enzyme activates its substrates, MI and O2, at a carboxylate-bridged nonheme diiron(II/III) cluster, making it the first of many known nonheme diiron oxygenases to employ the mixed-valent form of its cofactor. Evidence suggests that (1) the Fe(III) site coordinates MI via its C1 and C6 hydroxyl groups, (2) the Fe(II) site reversibly coordinates O2 to produce a superoxo-diiron(III/III) intermediate, and (3) the pendant oxygen atom of the superoxide ligand abstracts hydrogen from C1 to initiate the unique C-C-bond-cleaving, four-electron oxidation reaction. This review recounts the studies leading to the recognition of the novel cofactor requirement and catalytic mechanism of MIOX and forecasts how remaining gaps in our understanding might be filled by additional experiments. PMID:19173070

  5. Quality Improvements in the Early Care and Education Workforce: Outcomes and Impact of the T.E.A.C.H. Early Childhood[R] Project (United States)

    Miller, Joyce Ann; Bogatova, Tania


    To date there has not been a systematic, longitudinal research to assess the efficacy of public investments in the professional development of early childhood educators that are funded through the T.E.A.C.H. Early Childhood[R] Project. This study of the T.E.A.C.H. Early Childhood[R] Project Pennsylvania provides a longitudinal analysis of the data…

  6. Iridium-Catalyzed Direct C-H Sulfamidation of Aryl Nitrones with Sulfonyl Azides at Room Temperature. (United States)

    Pi, Chao; Cui, Xiuling; Wu, Yangjie


    Ir(III)-catalyzed direct C-H sulfamidation of aryl nitrones has been developed to synthesize various sulfamidated nitrones in moderate to excellent yields with excellent regioselectivity and broad functional group tolerance. This transformation could proceed smoothly at room temperature with low catalyst loading in the absence of external oxidants, acids, or bases. Molecular nitrogen was released as the sole byproduct, thus providing an environmentally benign sulfamidation process. And this protocol could efficiently apply to synthesize the substituted benzisoxazoline via one-step transformation from the product.

  7. Carboxylate-Assisted Iridium-Catalyzed C-H Amination of Arenes with Biologically Relevant Alkyl Azides. (United States)

    Zhang, Tao; Hu, Xuejiao; Wang, Zhen; Yang, Tiantian; Sun, Hao; Li, Guigen; Lu, Hongjian


    An iridium-catalyzed C-H amination of arenes with a wide substrate scope is reported. Benzamides with electron-donating and -withdrawing groups and linear, branched, and cyclic alkyl azides are all applicable. Cesium carboxylate is crucial for both reactivity and regioselectivity of the reactions. Many biologically relevant molecules, such as amino acid, peptide, steroid, sugar, and thymidine derivatives can be introduced to arenes with high yields and 100 % chiral retention. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Palladium-Catalyzed Enantioselective C-H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization. (United States)

    Zhu, Yu-Chao; Li, Yan; Zhang, Bo-Chao; Zhang, Feng-Xu; Yang, Yi-Nuo; Wang, Xi-Sheng


    The first example of Pd II -catalyzed enantioselective C-H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) through both desymmetrization and parallel kinetic resolution (PKR). This is the first report of Pd II -catalyzed enantioselective C(sp 2 )-H functionalization through PKR, and it represents a novel strategy to construct sulfur chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Fabrication of catalytic electrodes for molten carbonate fuel cells (United States)

    Smith, James L.


    A porous layer of catalyst material suitable for use as an electrode in a molten carbonate fuel cell includes elongated pores substantially extending across the layer thickness. The catalyst layer is prepared by depositing particulate catalyst material into polymeric flocking on a substrate surface by a procedure such as tape casting. The loaded substrate is heated in a series of steps with rising temperatures to set the tape, thermally decompose the substrate with flocking and sinter bond the catalyst particles into a porous catalytic layer with elongated pores across its thickness. Employed as an electrode, the elongated pores provide distribution of reactant gas into contact with catalyst particles wetted by molten electrolyte.

  10. Catalytic bioreactors and methods of using same (United States)

    Worden, Robert Mark; Liu, Yangmu Chloe


    Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

  11. 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 was evaluated.

  12. 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...

  13. Reactively co-sputter deposited a-C:H/Cr thin films: Material characteristics and optical properties

    International Nuclear Information System (INIS)

    Cheng, Hsin-Yen; Chiou, Jau-Wern; Ting, Jyh-Ming; Tzeng, Yonhua


    Various chromium-containing amorphous hydrogenated carbon (a-C:H/Cr) coatings were deposited on oxygen-free copper and silicon substrates for use as solar selective absorber coatings. The deposition was performed using a magnetron co-sputter deposition method under various methane/Ar ratios, ranging from 0 to 8%. The obtained films were characterized using glazing incident X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, secondary ion mass spectrometer, and X-ray photoelectron spectroscopy. The optical absorptance and emittance at 100 °C were determined using UV–vis-NIR spectroscopy and Fourier transform infrared spectrometry, respectively. Effects of the material characteristics on the optical properties are reported and discussed. - Highlights: ► a-C:H/Cr coatings were prepared using reactive magnetron co-sputtering deposition. ► Cr exists as crystallites having diameters in between 1 to 2 nm. ► Coating prepared with 3% methane in the gas fed exhibits the best optical absorptance

  14. Reactively co-sputter deposited a-C:H/Cr thin films: Material characteristics and optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Hsin-Yen [Department of Materials Science and Engineering, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Chiou, Jau-Wern [Department of Applied Physics, National University of Kaohsiung, Kaohsiung University Rd., Nanzih District, Kaohsiung 811, Taiwan (China); Ting, Jyh-Ming, E-mail: [Department of Materials Science and Engineering, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Institute of Nanotechnology and Microsystems Engineer, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Center for Micro/Nano Science and Technology, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Tzeng, Yonhua [Institute of Nanotechnology and Microsystems Engineer, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Center for Micro/Nano Science and Technology, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Department of Electrical Engineering, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China)


    Various chromium-containing amorphous hydrogenated carbon (a-C:H/Cr) coatings were deposited on oxygen-free copper and silicon substrates for use as solar selective absorber coatings. The deposition was performed using a magnetron co-sputter deposition method under various methane/Ar ratios, ranging from 0 to 8%. The obtained films were characterized using glazing incident X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, secondary ion mass spectrometer, and X-ray photoelectron spectroscopy. The optical absorptance and emittance at 100 °C were determined using UV–vis-NIR spectroscopy and Fourier transform infrared spectrometry, respectively. Effects of the material characteristics on the optical properties are reported and discussed. - Highlights: ► a-C:H/Cr coatings were prepared using reactive magnetron co-sputtering deposition. ► Cr exists as crystallites having diameters in between 1 to 2 nm. ► Coating prepared with 3% methane in the gas fed exhibits the best optical absorptance.

  15. Collaborative Research: Nanopore Confinement of C-H-O Mixed Volatile Fluids Relevant to Subsurface Energy Systems

    Energy Technology Data Exchange (ETDEWEB)

    Grady, Brian P. [Univ. of Oklahoma, Norman, OK (United States)


    The scientific objective of this proposal was to obtain a fundamental atomic- to macro-scale understanding of the sorptivity, structure and dynamics of simple and complex hydrocarbon (HC) fluids at mineral surfaces or within nanoporous matrices over temperatures, pressures and compositions encountered in near-surface and shallow crustal environments. The research supported by this award was complementary to that conducted by the group of Prof. David cole at Ohio State University. The scope of the present award was to utilize molecular-level modeling to provide critically important insights into the interfacial properties of mineral-volatile systems, assist in the interpretation of experimental data and predict fluid behavior beyond the limits of current experimental capability. During the past three years the effort has focused primarily on the behavior of C-H volatiles including methane (CH4) and propane (C3H8), mixed-volatile systems including hydrocarbon - CO2 with and without H2O present. The long-range goal is to quantitatively link structure, dynamics and reactivity in complex mineral-/C-H-O systems from the atomic to the molecular to the macroscopic levels. The results are relevant to areas of growing importance such as gas shale, HC-bearing hydrothermal systems, and CO2 storage.

  16. Catalytic Decoupling of Quantum Information

    DEFF Research Database (Denmark)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric


    The decoupling technique is a fundamental tool in quantum information theory with applications ranging from quantum thermodynamics to quantum many body physics to the study of black hole radiation. In this work we introduce the notion of catalytic decoupling, that is, decoupling in the presence...... of an uncorrelated ancilla system. This removes a restriction on the standard notion of decoupling, which becomes important for structureless resources, and yields a tight characterization in terms of the max-mutual information. Catalytic decoupling naturally unifies various tasks like the erasure of correlations...

  17. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne


    Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...

  18. Shape Bonding method (United States)

    Pontius, James T. (Inventor)


    The present invention is directed to a method of bonding at least two surfaces together. The methods step of the present invention include applying a strip of adhesive to a first surface along a predefined outer boundary of a bond area and thereby defining a remaining open area there within. A second surface, or gusset plate, is affixed onto the adhesive before the adhesive cures. The strip of adhesive is allowed to cure and then a second amount of adhesive is applied to cover the remaining open area and substantially fill a void between said first and second surfaces about said bond area. A stencil may be used to precisely apply the strip of adhesive. When the strip cures, it acts as a dam to prevent overflow of the subsequent application of adhesive to undesired areas. The method results in a precise bond area free of undesired shapes and of a preferred profile which eliminate the drawbacks of the prior art bonds.

  19. 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...

  20. 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...... 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...... bonds. The purpose is further to analyse the tax consequences of issuing bonds in both a direct issue of bonds and through securitization....

  1. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    ... improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is discussed. Some examples where performance enhancement was realized by catalyst design, appropriate choice of reactor, better injection and dispersion strategies ...

  2. Catalytic properties of niobium compounds

    International Nuclear Information System (INIS)

    Tanabe, K.; Iizuka, T.


    The catalytic activity and selectivity of niobium compounds including oxides, salts, organometallic compounds and others are outlined. The application of these compounds as catalysts to diversified reactions is reported. The nature and action of niobium catalysts are characteristic and sometimes anomalous, suggesting the necessity of basic research and the potential use as catalysts for important processes in the chemical industry. (Author) [pt

  3. Catalytic carboxyester hydrolysis by diaminodiphenols

    Indian Academy of Sciences (India)


    Two diaminodiphenols, 1 and 2, have been examined as catalysts for the hydrolysis of 4- nitrophenyl acetate (NA) and 4-nitrophenylphosphate (NP) in aqueous-acetonitrile (25% acetonitrile v/v) media at 35ºC, I = 1·0 mol dm–3. The compound 1 enhances the hydrolysis rate of NA more than 105 times. Its catalytic efficiency ...

  4. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    on selectivity can make substantial impact on process viability and economics. Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so ...

  5. Bond lengths in organic and metal-organic compounds revisited: X-H bond lengths from neutron diffraction data. (United States)

    Allen, Frank H; Bruno, Ian J


    The number of structures in the Cambridge Structural Database (CSD) has increased by an order of magnitude since the preparation of two major compilations of standard bond lengths in mid-1985. It is now of interest to examine whether this huge increase in data availability has implications for the mean bond-length values published in the late 1980s. Those compilations reported mean X-H bond lengths derived from rather sparse information and for rather few chemical environments. During the intervening years, the number of neutron studies has also increased, although only by a factor of around 2.25, permitting a new analysis of X-H bond-length distributions for (a) organic X = C, N, O, B, and (b) a variety of terminal and homometallic bridging transition metal hydrides. New mean values are reported here and are compared with earlier results. These new overall means are also complemented by an analysis of X-H distances at lower temperatures (T chemical environments for which statistically acceptable mean X-H bond lengths can be obtained, although values from individual structures are also collated to further extend the chemical range of this compilation. Updated default 'neutron-normalization' distances for use in hydrogen-bond and deformation-density studies are also proposed for C-H, N-H and O-H, and the low-temperature analysis provides specific values for certain chemical environments and hybridization states of X.

  6. C-H activation with elemental sulfur: synthesis of cyclic thioureas from formaldehyde aminals and S8. (United States)

    Denk, M K; Gupta, S; Brownie, J; Tajammul, S; Lough, A J


    The C-H activation of cyclic formaldehyde aminals LCH2 (L = RN-CH2CH2CH2-NR and RNCH2CH2-NR, R = Me, Et, iPr, tBu, or Ph) with S8 proceeds at unusually low temperatures (TS8 was investigated. 1,3-Dithiolane is cleanly converted into 1,3-dithiolane-2-thione (S8, 14 d, 190 degrees C) and resembles the cyclic formaldehyde aminals in this respect. 1,3-Dioxolane (L = OCH2CH2O) is completely inert towards sulfur even under forceful reaction conditions (190 degrees C, 14 d). The formation of thioureas from aminals was investigated at the CBS-4 and B3LYP/6-31G(d) levels of theory.

  7. Fields, particles and analyticity: recent results or 30 goldberg (ER) variations on B.A.C.H

    International Nuclear Information System (INIS)

    Bros, J.


    As it is known, Axiomatic Field Theory (A) implies double analyticity of the η-point functions in space-time and energy-momentum Complex Variables (C), with various interconnections by Fourier-Laplace analysis. When the latter is replaced by. Harmonic Analysis (H) on spheres and hyperboloids, a new kind of double analyticity results from (A) (i.e. from locality, spectral condition, temperateness and invariance): complex angular momentum is thereby introduced (a missing chapter in (A)). Exploitation of Asymptotic Completeness via Bethe-Salpeter-type equations (B) leads to new developments of the previous theme on (A, C, H) (complex angular momentum) and of other themes on (A,C) (crossing, Haag-Swieca property etc...). Various aspects of (A) + (B) have been implemented in Constructive Field Theory (composite spectrum, asymptotic properties etc...) by a combination of specific techniques and of model-independent methods

  8. Palladium-Catalyzed Zinc-Amide-Mediated C-H Arylation of Fluoroarenes and Heteroarenes with Aryl Sulfides. (United States)

    Otsuka, Shinya; Yorimitsu, Hideki; Osuka, Atsuhiro


    C-H arylation of polyfluoroarenes and heteroarenes with aryl sulfides proceeds smoothly with the aid of a palladium-N-heterocyclic carbene catalyst. A bulky zinc amide, TMPZnCl⋅LiCl, plays a key role as an effective base to generate the corresponding arylzinc species in situ. This arylation protocol is practically much easier to perform than our previous method, which necessitates preparation of the arylzinc reagents in advance from the corresponding aryl halides. Aryl sulfides that are prepared through sulfur-specific reactions, such as SN Ar sulfanylation and extended Pummerer reactions, undergo this direct arylation, offering interesting transformations that are otherwise difficult to achieve with conventional halogen-based organic synthesis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Regioselective C-H hydroxylation of omeprazole sulfide by Bacillus megaterium CYP102A1 to produce a human metabolite. (United States)

    Jang, Hyun-Hee; Ryu, Sang-Hoon; Le, Thien-Kim; Doan, Tiep Thi My; Nguyen, Thi Huong Ha; Park, Ki Deok; Yim, Da-Eun; Kim, Dong-Hyun; Kang, Choong-Kyung; Ahn, Taeho; Kang, Hyung-Sik; Yun, Chul-Ho


    To find a simple enzymatic strategy for the efficient synthesis of the expensive 5'-hydroxyomeprazole sulfide, a recently identified minor human metabolite, from omeprazole sulfide, which is an inexpensive substrate. The practical synthetic strategy for the 5'-OH omeprazole sulfide was accomplished with a set of highly active CYP102A1 mutants, which were obtained by blue colony screening from CYP102A1 libraries with a high conversion yield. The mutant and even the wild-type enzyme of CYP102A1 catalyzed the high regioselective (98 %) C-H hydroxylation of omeprazole sulfide to 5'-OH omeprazole sulfide with a high conversion yield (85-90 %). A highly efficient synthesis of 5'-OH omeprazole sulfide was developed using CYP102A1 from Bacillus megaterium as a biocatalyst.

  10. Microwave-assisted extraction and a new determination method for total steroid saponins from Dioscorea zingiberensis C.H. Wright. (United States)

    Ren, Yao; Chen, Yu; Hu, Bohan; Wu, Hui; Lai, Furao; Li, Xiaofeng


    An efficient microwave-assisted extraction (MAE) technique was applied to isolate total steroid saponins from Dioscorea zingiberensis C.H. Wright (DZW). The optimal extracting conditions were established as 75% ethanol as solvent, ratio of solid/liquid 1:20 (g/ml), temperature 75 °C, irradiation power 600 W and three extraction cycles of 6 min each. Scanning electron microscopy (SEM) images of DZW processed by four different extractions provided visual evidence of the disruption effect on DZW. Diosgenin was quantified by HPLC and examined further by LC-ESI/MS after acid hydrolysis. Total steroid saponins were calculated using diosgenin from total steroid saponins. The MAE procedure was optimized, validated and compared with other conventional extraction processes. This report provides a convenient technology for the extraction and quantification of total saponins of DZW combining MAE with HPLC and LC-ESI/MS for the first time. Copyright © 2015 Elsevier Inc. All rights reserved.

  11. Reduction-induced Double Bond Coordination and Multiple C-H Activation in Fully-substituted Titanocenes Bearing a Pendant Double Bond or an Eight-Membered Hydrocarbyl Ansa-Chain

    Czech Academy of Sciences Publication Activity Database

    Horáček, Michal; Štěpnička, P.; Kubišta, Jiří; Císařová, I.; Petrusová, Lidmila; Mach, Karel


    Roč. 667, 1/2 (2003), s. 154-166 ISSN 0022-328X R&D Projects: GA AV ČR IAA4040004; GA ČR GA203/02/0436 Institutional research plan: CEZ:AV0Z4040901 Keywords : titanocene * titanuim * X-ray crystallography Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.042, year: 2003

  12. Chemistry of Titan's Aerosols : Correlation of The C/n &C/h Ratios To Pressure and Temperature (United States)

    Bernard, J.-M.; Coll, P.; Raulin, F.

    The gas present in Titan's atmosphere are forming organics aerosols under action of the solar radiations and of electrons from Saturn's magnetosphere. Many experimental simulations are been realised by irradiating N2/CH4 gas mixtures with different en- ergy sources in order to reproduce the chemistry of gas and particulate phases (Thomp- son et al, 1991; Mc Donald et al, 1994; de Vanssay et al, 1995; McKay, 1996; Coll et al, 1997, 1998a,b; and Refs. included). Until very recently, only one organics re- mains detected in Titan but not in laboratory simulation : C4N2. A full program of experimental research has been developed at LISA, which was able to provide a com- plete identification of a wide range of compounds, proposed to be present in Titan's atmosphere, including C4N2. The composition of aerosol on Titan is not known, due to its complexity. Especially its building molecules are difficult to identify. Only functional groups of analogues have been determined using spectroscopy and pyrolysis. However this chemical composi- tion is a key parameter for Cassini-Huygens experiments and atmospheric modeling : even the optical properties of aerosols are related to C/N and C/H ratios. We will present the results of the variation of C/N and C/H ratios according to the temperature and the pressure in Titan's atmosphere simulations. This data will allow to constraint photochemical models, in order for them to be more realistic. Then the comprehension of the mechanism of aerosols formation on Titan as function of altitude will be easier.

  13. Three-Dimensional Structure and Catalytic Mechanism of Cytosine Deaminase

    Energy Technology Data Exchange (ETDEWEB)

    R Hall; A Fedorov; C Xu; E Fedorov; S Almo; F Raushel


    Cytosine deaminase (CDA) from E. coli is a member of the amidohydrolase superfamily. The structure of the zinc-activated enzyme was determined in the presence of phosphonocytosine, a mimic of the tetrahedral reaction intermediate. This compound inhibits the deamination of cytosine with a K{sub i} of 52 nM. The zinc- and iron-containing enzymes were characterized to determine the effect of the divalent cations on activation of the hydrolytic water. Fe-CDA loses activity at low pH with a kinetic pKa of 6.0, and Zn-CDA has a kinetic pKa of 7.3. Mutation of Gln-156 decreased the catalytic activity by more than 5 orders of magnitude, supporting its role in substrate binding. Mutation of Glu-217, Asp-313, and His-246 significantly decreased catalytic activity supporting the role of these three residues in activation of the hydrolytic water molecule and facilitation of proton transfer reactions. A library of potential substrates was used to probe the structural determinants responsible for catalytic activity. CDA was able to catalyze the deamination of isocytosine and the hydrolysis of 3-oxauracil. Large inverse solvent isotope effects were obtained on k{sub cat} and k{sub cat}/K{sub m}, consistent with the formation of a low-barrier hydrogen bond during the conversion of cytosine to uracil. A chemical mechanism for substrate deamination by CDA was proposed.

  14. Recyclable Nanostructured Catalytic Systems in Modern Environmentally Friendly Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Irina Beletskaya


    Full Text Available Modern chemical synthesis makes heavy use of different types of catalytic systems: homogeneous, heterogeneous and nano-sized. The latter – nano-sized catalysts – have given rise in the 21st century to a rapidly developing area of research encompassing several prospects and opportunities for new technologies. Catalytic reactions ensure high regio- and stereoselectivity of chemical transformations, as well as better yields and milder reaction conditions. In recent years several novel catalytic systems were developed for selective formation of carbon-heteroatom and carbon-carbon bonds. This review presents the achievements of our team in our studies on various types of catalysts containing metal nanoparticles: palladium-containing diblock copolymer micelles; soluble palladium-containing polymers; metallides on a support; polymeric metal salts and oxides; and, in addition, metal-free organic catalysts based on soluble polymers acting as nanoreactors. Representative examples are given and discussed in light of possible applications to solve important problems in modern organic synthesis.

  15. 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....

  16. Can laccases catalyze bond cleavage in lignin? (United States)

    Munk, Line; Sitarz, Anna K; Kalyani, Dayanand C; Mikkelsen, J Dalgaard; Meyer, Anne S


    Modification of lignin is recognized as an important aspect of the successful refining of lignocellulosic biomass, and enzyme-assisted processing and upcycling of lignin is receiving significant attention in the literature. Laccases (EC are taking the centerstage of this attention, since these enzymes may help degrading lignin, using oxygen as the oxidant. Laccases can catalyze polymerization of lignin, but the question is whether and how laccases can directly catalyze modification of lignin via catalytic bond cleavage. Via a thorough review of the available literature and detailed illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin model compounds; ii) For laccases to catalyze inter-unit bond cleavage in lignin substrates, the presence of a mediator system is required. Clearly, the higher the redox potential of the laccase enzyme, the broader the range of substrates, including o- and p-diphenols, aminophenols, methoxy-substituted phenols, benzenethiols, polyphenols, and polyamines, which may be oxidized. In addition, the currently available analytical methods that can be used to detect enzyme catalyzed changes in lignin are summarized, and an improved nomenclature for unequivocal interpretation of the action of laccases on lignin is proposed. Copyright © 2015 Elsevier Inc. All rights reserved.

  17. Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters. (United States)

    Manzoor, Dar; Pal, Sourav


    Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

  18. Probing the Catalytic Mechanism of S-Ribosylhomocysteinase (LuxS) with Catalytic Intermediates and Substrate Analogues

    Energy Technology Data Exchange (ETDEWEB)

    Gopishetty, Bhaskar; Zhu, Jinge; Rajan, Rakhi; Sobczak, Adam J.; Wnuk, Stanislaw F.; Bell, Charles E.; Pei, Dehua; (OSU); (FIU)


    S-Ribosylhomocysteinase (LuxS) cleaves the thioether bond in S-ribosylhomocysteine (SRH) to produce homocysteine (Hcys) and 4,5-dihydroxy-2,3-pentanedione (DPD), the precursor of the type II bacterial quorum sensing molecule (AI-2). The catalytic mechanism of LuxS comprises three distinct reaction steps. The first step involves carbonyl migration from the C1 carbon of ribose to C2 and the formation of a 2-ketone intermediate. The second step shifts the C=O group from the C2 to C3 position to produce a 3-ketone intermediate. In the final step, the 3-ketone intermediate undergoes a {beta}-elimination reaction resulting in the cleavage of the thioether bond. In this work, the 3-ketone intermediate was chemically synthesized and shown to be chemically and kinetically competent in the LuxS catalytic pathway. Substrate analogues halogenated at the C3 position of ribose were synthesized and reacted as time-dependent inhibitors of LuxS. The time dependence was caused by enzyme-catalyzed elimination of halide ions. Examination of the kinetics of halide release and decay of the 3-ketone intermediate catalyzed by wild-type and mutant LuxS enzymes revealed that Cys-84 is the general base responsible for proton abstraction in the three reaction steps, whereas Glu-57 likely facilitates substrate binding and proton transfer during catalysis.

  19. Probing the Catalytic Mechanism of S-Ribosylhomocysteinase (LuxS) with Catalytic Intermediates and Substrate Analogues

    International Nuclear Information System (INIS)

    Gopishetty, Bhaskar; Zhu, Jinge; Rajan, Rakhi; Sobczak, Adam J.; Wnuk, Stanislaw F.; Bell, Charles E.; Pei, Dehua


    S-Ribosylhomocysteinase (LuxS) cleaves the thioether bond in S-ribosylhomocysteine (SRH) to produce homocysteine (Hcys) and 4,5-dihydroxy-2,3-pentanedione (DPD), the precursor of the type II bacterial quorum sensing molecule (AI-2). The catalytic mechanism of LuxS comprises three distinct reaction steps. The first step involves carbonyl migration from the C1 carbon of ribose to C2 and the formation of a 2-ketone intermediate. The second step shifts the C=O group from the C2 to C3 position to produce a 3-ketone intermediate. In the final step, the 3-ketone intermediate undergoes a β-elimination reaction resulting in the cleavage of the thioether bond. In this work, the 3-ketone intermediate was chemically synthesized and shown to be chemically and kinetically competent in the LuxS catalytic pathway. Substrate analogues halogenated at the C3 position of ribose were synthesized and reacted as time-dependent inhibitors of LuxS. The time dependence was caused by enzyme-catalyzed elimination of halide ions. Examination of the kinetics of halide release and decay of the 3-ketone intermediate catalyzed by wild-type and mutant LuxS enzymes revealed that Cys-84 is the general base responsible for proton abstraction in the three reaction steps, whereas Glu-57 likely facilitates substrate binding and proton transfer during catalysis.

  20. Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic Hydroaminoalkylation Reactions

    KAUST Repository

    Hamzaoui, Bilel


    Intermolecular catalytic hydroaminoalkylation of unactivated alkene occurs with silica-supported azazirconacyclopropane [[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)(η2-NMeCH2)(NMe2)]. Mechanistic studies were conducted using surface organometallic chemistry (SOMC) concepts to identify the key surface intermediates. The azametallacyclopentene intermediate {[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)[η2-NMeCH2CH(Me)CH2](NMe2)} was isolated after treating with 1-propylene and characterized by FT-IR spectroscopy, elemental analysis, 1H 13C HETCOR, DARR SS-NMR and DQ TQ SS-NMR. The regeneration of the catalyst was conducted by dimethylamine protonolysis to yield the pure amine.

  1. Quinoline-2-carboimine copper complex immobilized on amine functionalized silica coated magnetite nanoparticles: a novel and magnetically retrievable catalyst for the synthesis of carbamates via C-H activation of formamides. (United States)

    Sharma, R K; Dutta, Sriparna; Sharma, Shivani


    In the present study, we report the synthesis of a highly efficient and magnetically retrievable catalytic system (Cu-2QC@Am-SiO2@Fe3O4) through the covalent immobilization of quinoline-2-carboxaldehyde (2QC) on an amine functionalized silica coated ferrite nanosupport followed by metallation with copper acetate. The structure of the organic-inorganic hybrid nanomaterial has been confirmed using various physicochemical techniques such as Powder X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy Dispersive X-Ray Spectroscopy (EDS), Energy Dispersive X-Ray Fluorescence Spectroscopy (ED-XRF), Atomic Absorption Spectroscopy (AAS), Inductively Coupled Plasma Spectroscopy (ICP) and Vibrating Sample Magnetometry (VSM). The resulting nanocatalyst exhibits a remarkable catalytic efficacy in the synthesis of industrially and pharmaceutically significant carbamates via the C-H activation of formamides under solvent free conditions. The most important attribute of the present methodology is that the catalyst can be recovered simply through an external magnetic force and reused several times without any significant deterioration in its activity. Furthermore, the heterogeneity test has been carried out in order to ensure the intrinsic stability of the nanostructured catalyst. The activity of the Cu-2QC@Am-SiO2@Fe3O4 nanocatalyst has been found to be far more superior in comparison with the literature precedents in terms of the product yield, cost and reusability of the catalyst. Besides, ambient reaction conditions, simple workup procedure, wide substrate scope and cost effectiveness are some of the other outstanding features of this protocol that make it economical and sustainable.

  2. C–H Bond activation of methane with gaseous [(CH3)Pt(L)]+ complexes (L = pyridine, bipyridine, and phenanthroline)

    Czech Academy of Sciences Publication Activity Database

    Butschke, B.; Schlangen, M.; Schwarz, H.; Schröder, Detlef

    62b, č. 3 (2007), s. 309-311 ISSN 0932-0776 Grant - others:Deutsche Forschungsgemeinschaft(DE) SFB546 Institutional research plan: CEZ:AV0Z40550506 Keywords : C-H bond activation * electrospray ionization * mass spectrometry * methane * platinum Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.770, year: 2007

  3. Comprehensive Mechanistic Insight into Cooperative Lewis Acid/Cp*CoIII-Catalyzed C-H/N-H Activation for the Synthesis of Isoquinolin-3-ones. (United States)

    Wang, Qiong; Huang, Fang; Jiang, Langhuan; Zhang, Chuanxue; Sun, Chuanzhi; Liu, Jianbiao; Chen, Dezhan


    The mechanism of B(C 6 F 5 ) 3 promoted Cp*Co III -catalyzed C-H functionalization was investigated in detail employing density functional theory (DFT). The formation free energy of every possible species in the multicomponent complex system was explored and the optimal active catalyst was screened out. The results uncover the role of B(C 6 F 5 ) 3 played in forming active catalyst is from the coordination with OAc - , but not from the formation of [I(C 6 F 5 ) 3 B] - , and no acceleration effect is found in C-H activation as well as the formation of Co III -carbene intermediate. Moreover, present theoretical results elucidate the Cp*Co III -catalyzed C-H activation is mediated by imine N-coordination other than general proposed the sequence of N-deprotonation directed C-H activation. The metal-controlled C-H/N-H selectivity was then elucidated by insighting into [Cp*Co III OAc] + /[Cp*Rh III OAc] + -catalyzed C-H and N-H activations, respectively.

  4. Chemisorption bonding and catalysis

    International Nuclear Information System (INIS)

    Danese, J.B.; Schrieffer, J.R.


    The general features of the LCAO--MO, Green's function, and multiple-scattering chi α methods and their applications to surfaces and surface-related problems are discussed. Emphasis is placed on the localization of bonding in surface complexes

  5. Tile-bonding tool (United States)

    Haynie, C. C.; Holt, J. W.


    Device applies uniform, constant, precise pressure to hold tiles in place during bonding. Tool consists of pressure bladders supported by adjustable pole. Pole can accomodate single or multiple bladders. Tiles can be flat or contoured.

  6. Bond markets in Africa

    Directory of Open Access Journals (Sweden)

    Yibin Mu


    Full Text Available African bond markets have been steadily growing in recent years, but nonetheless remain undeveloped. African countries would benefit from greater access to financing and deeper financial markets. This paper compiles a unique set of data on government securities and corporate bond markets in Africa. It then applies an econometric model to analyze the key determinants of African government securities market and corporate bond market capitalization. Government securities market capitalization is directly related to better institutions and interest rate volatility, and inversely related to smaller fiscal deficits, higher interest rate spreads, exchange rate volatility, and current and capital account openness. Corporate bond market capitalization is directly linked to economic size, the level of development of the economy and financial markets, better institutions, and interest rate volatility, and inversely related to higher interest rate spreads and current account openness. Policy implications follow.

  7. Aliphatic C-C Bond Cleavage in α-Hydroxy Ketones by a Dioxygen-Derived Nucleophilic Iron-Oxygen Oxidant. (United States)

    Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K


    A nucleophilic iron-oxygen oxidant, formed in situ in the reaction between an iron(II)-benzilate complex and O 2 , oxidatively cleaves the aliphatic C-C bonds of α-hydroxy ketones. In the cleavage reaction, α-hydroxy ketones without any α-C-H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C-C bond of 17-α-hydroxyprogesterone affording androstenedione and acetic acid. The O 2 -dependent aliphatic C-C bond cleavage of α-hydroxy ketones containing no α-C-H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. On hydrogen bonding in 1,6-anhydro-beta-D-glucopyranose (levoglucosan): X-ray and neutron diffraction and DFT study. (United States)

    Smrcok, Lubomír; Sládkovicová, Mariana; Langer, Vratislav; Wilson, Chick C; Koós, Miroslav


    The geometry of hydrogen bonds in 1,6-anhydro-beta-D-glucopyranose (levoglucosan) is accurately determined by refinement of time-of-flight neutron single-crystal diffraction data. Molecules of levoglucosan are held together by a hydrogen-bond array formed by a combination of strong O-H...O and supporting weaker C-H...O bonds. These are fully and accurately detailed by the neutron diffraction study. The strong hydrogen bonds link molecules in finite chains, with hydroxyl O atoms acting as both donors and acceptors of hydroxyl H atoms. A comparison of molecular and solid-state DFT calculations predicts red shifts of O-H and associated blue shifts of C-H stretching frequencies due to the formation of hydrogen bonds in this system.

  9. Vapor Phase Catalytic Ammonia Reduction (United States)

    Flynn, Michael T.; Harper, Lynn D. (Technical Monitor)


    This paper discusses the development of a Vapor Phase Catalytic Ammonia Reduction (VPCAR) teststand and the results of an experimental program designed to evaluate the potential of the technology as a water purification process. In the experimental program the technology is evaluated based upon product water purity, water recovery rate, and power consumption. The experimental work demonstrates that the technology produces high purity product water and attains high water recovery rates at a relatively high specific power consumption. The experimental program was conducted in 3 phases. In phase I an Igepon(TM) soap and water mixture was used to evaluate the performance of an innovative Wiped-Film Rotating-Disk evaporator and associated demister. In phase II a phenol-water solution was used to evaluate the performance of the high temperature catalytic oxidation reactor. In phase III a urine analog was used to evaluate the performance of the combined distillation/oxidation functions of the processor.

  10. Handbook of wafer bonding

    CERN Document Server

    Ramm, Peter; Taklo, Maaike M V


    Written by an author and editor team from microsystems companies and industry-near research organizations, this handbook and reference presents dependable, first-hand information on bonding technologies.In the first part, researchers from companies and institutions around the world discuss the most reliable and reproducible technologies for the production of bonded wafers. The second part is devoted to current and emerging applications, including microresonators, biosensors and precise measuring devices.

  11. Diffusion bonding techniques

    International Nuclear Information System (INIS)

    Peters, R.D.


    The applications of diffusion bonding at the General Electric Neutron Devices Department are briefly discussed, with particular emphasis on the gold/gold or gold/indium joints made between metallized alumina ceramic parts in the vacuum switch tube and the crystal resonator programs. Fixtures which use the differential expansion of dissimilar metals are described and compared to one that uses hydraulic pressure to apply the necessary bonding force

  12. Inorganic membranes and catalytic reactors


    Rangel, Maria do Carmo


    Membrane reactors are reviewed with emphasis in their applications in catalysis field. The basic principles of these systems are presented as well as a historical development. The several kinds of catalytic membranes and their preparations are discussed including the problems, needs and challenges to be solved in order to use these reactors in commercial processes. Some applications of inorganic membrane reactors are also shown. It was concluded that these systems have a great potential for i...

  13. Catalytic strategy used by the myosin motor to hydrolyze ATP. (United States)

    Kiani, Farooq Ahmad; Fischer, Stefan


    Myosin is a molecular motor responsible for biological motions such as muscle contraction and intracellular cargo transport, for which it hydrolyzes adenosine 5'-triphosphate (ATP). Early steps of the mechanism by which myosin catalyzes ATP hydrolysis have been investigated, but still missing are the structure of the final ADP·inorganic phosphate (Pi) product and the complete pathway leading to it. Here, a comprehensive description of the catalytic strategy of myosin is formulated, based on combined quantum-classical molecular mechanics calculations. A full exploration of catalytic pathways was performed and a final product structure was found that is consistent with all experiments. Molecular movies of the relevant pathways show the different reorganizations of the H-bond network that lead to the final product, whose γ-phosphate is not in the previously reported HPγO4(2-) state, but in the H2PγO4(-) state. The simulations reveal that the catalytic strategy of myosin employs a three-pronged tactic: (i) Stabilization of the γ-phosphate of ATP in a dissociated metaphosphate (PγO3(-)) state. (ii) Polarization of the attacking water molecule, to abstract a proton from that water. (iii) Formation of multiple proton wires in the active site, for efficient transfer of the abstracted proton to various product precursors. The specific role played in this strategy by each of the three loops enclosing ATP is identified unambiguously. It explains how the precise timing of the ATPase activation during the force generating cycle is achieved in myosin. The catalytic strategy described here for myosin is likely to be very similar in most nucleotide hydrolyzing enzymes.

  14. The charge density distribution in a model compound of the catalytic triad in serine proteases. (United States)

    Overgaard, J; Schiøtt, B; Larsen, F K; Iversen, B B


    Combined low temperature (28(1) K) X-ray and neutron diffraction measurements were carried out on the co-crystallised complex of betaine, imidazole, and picric acid (1). The experimental charge density was determined and compared with ab initio theoretical calculations at the B3LYP/6-311G(d,p) level of theory. The complex serves as a model for the active site in, for example, the serine protease class of enzymes, the so-called catalytic triad. The crystal contains three short strong N-H...O hydrogen bonds (HBs) with dN...O comparison with low-barrier and single-well hydrogen bonding systems (e.g., benzoylacetone and nitromalonamide) shows that the low-barrier hydrogen bond (LBHB) state is characterized by an enormously increased hydrogen atom source contribution to the bond critical point in the HB. In this context, HB2 can be characterized as intermediate between localized HBs and delocalized LBHBs.

  15. Iron-catalysed fluoroaromatic coupling reactions under catalytic modulation with 1,2-bis(diphenylphosphino)benzene. (United States)

    Hatakeyama, Takuji; Kondo, Yoshiyuki; Fujiwara, Yu-Ichi; Takaya, Hikaru; Ito, Shingo; Nakamura, Eiichi; Nakamura, Masaharu


    A catalytic amount of 1,2-bis(diphenylphosphino)benzene (DPPBz) achieves selective cleavage of sp(3)-carbon-halogen bond in the iron-catalysed cross-coupling between polyfluorinated arylzinc reagents and alkyl halides, which was unachievable with a stoichiometric modifier such as TMEDA; the selective iron-catalysed fluoroaromatic coupling provides easy and practical access to polyfluorinated aromatic compounds.

  16. Catalytic mechanism and product specificity of cyclodextrin glycosyltransferase, a prototypical transglycosylase from the α-amylase family

    NARCIS (Netherlands)

    Uitdehaag, Joost C.M.; Veen, Bart A. van der; Dijkhuizen, Lubbert; Dijkstra, Bauke W.


    The catalytic mechanism of cyclodextrin glycosyltransferase, a member of the α-amylase family, is reviewed. The focus is put on the bond cleavage mechanism, the nature of the transition state and of the covalent intermediate, and on the stereo-electronic and lateral protonation contributions to

  17. Catalytic mechanism and product specificity of cyclodextrin glycosyltransferase, a prototypical transglycosylase from the alpha-amylase family

    NARCIS (Netherlands)

    Uitdehaag, JCM; van der Veen, BA; Dijkhuizen, L; Dijkstra, BW


    The catalytic mechanism of cyclodextrin glycosyltransferase, a member of the a-amylase family, is reviewed. The focus is put on the bond cleavage mechanism, the nature of the transition state and of the covalent intermediate, and on the stereo-electronic and lateral protonation contributions to

  18. Fundamentals of fiber bonding in thermally point-bonded nonwovens (United States)

    Chidambaram, Aparna

    Thermal point bonding (TPB) uses heat and pressure to bond a web of fibers at discrete points imparting strength to the manufactured fabric. This process significantly reduces the strength and elongation of the bridging fibers between bond points while strengthening the web. Single fiber experiments were performed with four structurally different polypropylene fibers to analyze the inter-relationships between fiber structure, fiber properties and bonding process. Two fiber types had a low birefringence sheath or surface layer while the remaining had uniform birefringence profiles through their thickness. Bonds were formed between isolated pairs of fibers by subjecting the fibers to a calendering process and simulating TPB process conditions. The dependence of bond strength on bonding temperature and on the type of fiber used was evaluated. Fiber strengths before and after bonding were measured and compared to understand the effect of bonding on fiber strength. Additionally, bonded fiber strength was compared to the strength of single fibers which had experienced the same process conditions as the bonded pairs. This comparison estimated the effect of mechanical damage from pressing fibers together with steel rolls while creating bonds in TPB. Interfiber bond strength increased with bonding temperature for all fiber types. Fiber strength decreased with increasing bonding temperature for all fiber types except for one type of low birefringent sheath fibers. Fiber strength degradation was unavoidable at temperatures required for successful bonding. Mechanical damage from compression of fibers between rolls was an insignificant factor in this strength loss. Thermal damage during bonding was the sole significant contributor to fiber strength degradation. Fibers with low birefringence skins formed strong bonds with minimal fiber strength loss and were superior to fibers without such surface layers in TPB performance. A simple model to predict the behavior of a two-bond

  19. Optical Characterization of Amorphous Hydrogenated Carbon (a-C:H) Thin Films Prepared by Single RF Plasma Method (United States)

    Dogan, Mansuroglu; Kadir, Goksen; Sinan, Bilikmen


    Methane (CH4) plasma was used to produce amorphous hydrogenated carbon (a-C:H) films by a single capacitively coupled radio frequency (RF) powered plasma system. The system consists of two parallel electrodes: the upper electrode is connected to 13.56 MHz RF power and the lower one is connected to the ground. Thin films were deposited on glass slides with different sizes and on silicon wafers. The influence of the plasma species on film characteristics was studied by changing the plasma parameters. The changes of plasma species during the deposition were investigated by optical emission spectroscopy (OES). The structural and optical properties were analyzed via Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and UV-visible spectroscopy, and the thicknesses of the samples were measured by a profilometer. The sp3/sp2 ratio and the existing H atoms play a significant role in the determination of the chemical properties of thin films in the plasma. The film quality and deposition rate were both increased by raising the power and the flow rate.

  20. Durability-enhanced two-dimensional hole gas of C-H diamond surface for complementary power inverter applications. (United States)

    Kawarada, Hiroshi; Yamada, Tetsuya; Xu, Dechen; Tsuboi, Hidetoshi; Kitabayashi, Yuya; Matsumura, Daisuke; Shibata, Masanobu; Kudo, Takuya; Inaba, Masafumi; Hiraiwa, Atsushi


    Complementary power field effect transistors (FETs) based on wide bandgap materials not only provide high-voltage switching capability with the reduction of on-resistance and switching losses, but also enable a smart inverter system by the dramatic simplification of external circuits. However, p-channel power FETs with equivalent performance to those of n-channel FETs are not obtained in any wide bandgap material other than diamond. Here we show that a breakdown voltage of more than 1600 V has been obtained in a diamond metal-oxide-semiconductor (MOS) FET with a p-channel based on a two-dimensional hole gas (2DHG). Atomic layer deposited (ALD) Al 2 O 3 induces the 2DHG ubiquitously on a hydrogen-terminated (C-H) diamond surface and also acts as both gate insulator and passivation layer. The high voltage performance is equivalent to that of state-of-the-art SiC planar n-channel FETs and AlGaN/GaN FETs. The drain current density in the on-state is also comparable to that of these two FETs with similar device size and V B .

  1. Copper-promoted methylene C-H oxidation to a ketone derivative by O2

    DEFF Research Database (Denmark)

    Deville, Claire; McKee, Vickie; McKenzie, Christine J.


    The methylene group of the ligand 1,2-di(pyridin-2-yl)-ethanone oxime (dpeo) is slowly oxygenated by the O2 in air under ambient conditions when [Cu(dpeo)2](ClO4)2 is dissolved in ethanol or acetonitrile. An initial transient ketone product, 2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone, (hidpe......) 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...

  2. Wide Spectral Sensitivity of Monolithic a-SiC:H pi’n/pin Photodiode Outside the Visible Spectrum

    Directory of Open Access Journals (Sweden)

    Manuela Vieira


    Full Text Available In this paper, we experimentally demonstrate the use of near-ultraviolet steady state illumination to increase the spectral sensitivity of a double a-SiC/Si pi’n/pin photodiode beyond the visible spectrum (400 nm-880 nm. The concept is extended to implement a 1 by 4 wavelength division multiplexer with channel separation in the visible/near infrared ranges. The device consists of a p-i'(a-SiC:H-n/p-i(a-Si:H-n heterostructure, sandwiched between two transparent contacts. Optoelectronic characterization of the device is presented and shows the feasibility of tailoring the wavelength and bandwidth of a polychromatic mixture of different wavelengths. Results show that the spectral current under steady state ultraviolet irradiation depends strongly on the wavelength of the impinging light, and on the background intensity and irradiation side allowing controlled high-pass filtering properties. If several monochromatic pulsed lights, in the visible/near infrared (VIS/NIR range, separately or in a polychromatic mixture illuminate the device, data shows that, front background enhances the light-to-dark sensitivity of the medium, long and infrared wavelength channels, and quench strongly the low wavelengths channels. Back background has the opposite behavior; it enhances only channel magnitude in short wavelength range and strongly reduces it in the long ones. This nonlinearity provides the possibility for selective tuning of a specific wavelength. A capacitive optoelectronic model supports the experimental results. A numerical simulation is presented.

  3. Surface morphology and grain analysis of successively industrially grown amorphous hydrogenated carbon films (a-C:H) on silicon (United States)

    Catena, Alberto; McJunkin, Thomas; Agnello, Simonpietro; Gelardi, Franco M.; Wehner, Stefan; Fischer, Christian B.


    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 sp2 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 sp2 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.

  4. A novel glycosylated solution from Dioscorea zingiberensis C.H. Wright significantly improves the solvent productivity of Clostridium beijerinckii. (United States)

    Xiao, Chuan; Fan, Wei; Du, Shengjie; Liu, Laizhuang; Wang, Changli; Guo, Mengzhen; Zhang, Liwei; Zhang, Meng; Yu, Longjiang


    The economics of bio-solvent production are largely dependent on the cost of the fermentation substrate. Dioscorea zingiberensis C.H. Wright (DZW), the main raw material used to produce saponin, contains 13-18% starch which can be directly saccharified to a saccharification liquid of DZW starch (SLDS) that contains abundant nutrients. In this study, the water-soluble micromolecule compounds in SLDS were quantified through 1 H NMR. Using SLDS as the substrate to conduct ABE fermentation by Clostridium beijerinckii, the fermentation cycle was shortened 24h, the maximum biomass and consumption rate of the glucose significantly increased, and the productivity of total solvents were increased by 0.244±0.010g/L/h compared to standard P 2 medium. Expression analysis of genes encoding key enzymes involved in acetone and butanol production and glucose consumption showed that they were induced by SLDS. Taken together, SLDS is a useful and renewable glycosylated solution for ABE fermentation. Copyright © 2017. Published by Elsevier Ltd.

  5. Synthesis and characterization of tantalum organometallic complexes. Catalytic activity for olefins

    International Nuclear Information System (INIS)

    Baley, A.S.


    Synthesis of monoaryloxy (alcoxy) neopentyl compounds is investigated. The tantalum-oxygen bond is formed by two parallel ways from TaCl 5 or TaR 2 Cl 3 with R = neopentyl and the tantalum carbon bond from a neopentyl derivative of the main series. Some compounds were isolated and characterized by NMR, elemental analysis and sometimes X-ray structure, some others are characterized in solution only. Catalytic effect is tested by ethylene dimerization and olefin polymerization. Reactivity of tantalum aryloxy neopentyl in respect to complexing and chelating ligands is studied for preparation of neopentylidene complexes

  6. Theoretical evidence for bond stretch isomerism in Grubbs olefin metathesis. (United States)

    Remya, Premaja R; Suresh, Cherumuttathu H


    A comprehensive density functional theory study on the dissociative and associative mechanisms of Grubbs first and second generation olefin metathesis catalysis reveals that ruthenacyclobutane intermediate (RuCB) observed in the Chauvin mechanism is not unique as it can change to a non-metathetic ruthenacyclobutane (RuCB') via the phenomenon of bond stretch isomerism (BSI). RuCB and RuCB' differ mainly in RuC α , RuC β , and C α C β bond lengths of the metallacycle. RuCB is metathesis active due to the agostic type bonding-assisted simultaneous activation of both C α C β bonds, giving hypercoordinate character to C β whereas an absence of such bonding interactions in RuCB' leads to typical CC single bond distances and metathesis inactivity. RuCB and RuCB' are connected by a transition state showing moderate activation barrier. The new mechanistic insights invoking BSI explains the non-preference of associative mechanism and the requirement of bulky ligands in the Grubbs catalyst design. The present study lifts the status of BSI from a concept of largely theoretical interest to a phenomenon of intense importance to describe an eminent catalytic reaction. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  7. α-Halo Amides as Competent Latent Enolates: Direct Catalytic Asymmetric Mannich-Type Reaction. (United States)

    Sun, Bo; Balaji, Pandur Venkatesan; Kumagai, Naoya; Shibasaki, Masakatsu


    α-Halogenated carbonyl compounds are susceptible to dehalogenation and thus largely neglected as enolate precursors in catalytic enantioselective C-C bond-forming reactions. By merging the increased stability of the α-C-halogen bond of amides and the direct enolization methodology of the designed amide, we explored a direct catalytic asymmetric Mannich-type reaction of α-halo 7-azaindoline amides with N-carbamoyl imines. All α-halo substituents, α-F, -Cl, -Br, -I amides, were tolerated to provide the Mannich-adducts in a highly stereoselective manner without undesirable dehalogenation. The diastereoselectivity switched intriguingly depending on the substitution pattern of the aromatic imines, which is ascribed to stereochemical differentiation based on the open transition-state model. Functional group interconversion of the 7-azaindoline amide moiety of the Mannich-adducts and further elaboration into a diamide without dehalogenation highlight the synthetic utility of the present protocol for accessing enantioenriched halogenated chemical entities.

  8. An Iron-Catalyzed Bond-Making/Bond-Breaking Cascade Merges Cycloisomerization and Cross-Coupling Chemistry. (United States)

    Echeverria, Pierre-Georges; Fürstner, Alois


    Treatment of readily available enynes with alkyl-Grignard reagents in the presence of catalytic amounts of Fe(acac)3 engenders a remarkably facile and efficient reaction cascade that results in the net formation of two new C-C bonds while a C-Z bond in the substrate backbone is broken. Not only does this new manifold lend itself to the extrusion of heteroelements (Z=O, NR), but it can even be used for the cleavage of activated C-C bonds. The reaction likely proceeds via metallacyclic intermediates, the iron center of which gains ate character before reductive elimination occurs. The overall transformation represents a previously unknown merger of cycloisomerization and cross-coupling chemistry. It provides ready access to highly functionalized 1,3-dienes comprising a stereodefined tetrasubstituted alkene unit, which are difficult to make by conventional means. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Catalytic Reforming of Lignin-Derived Bio-Oil Over a Nanoporous Molecular Sieve Silicoaluminophosphate-11. (United States)

    Park, Y K; Kang, Hyeon Koo; Jang, Hansaem; Suh, Dong Jin; Park, Sung Hoon


    Catalytic pyrolysis of lignin, a major constituent of biomass, was performed. A nanoporous molecular sieve silicoaluminophosphate-11 (SAPO-11) was selected as catalyst. Thermogravimetric analysis showed that 500 degrees C was the optimal pyrolysis temperature. Pyrolyzer-gas chromatography/mass spectroscopy was used to investigate the pyrolysis product distribution. Production of phenolics, the dominant product from the pyrolysis of lignin, was promoted by the increase in the catalyst dose. In particular, low-molecular-mass phenolics were produced more over SAPO-11, while high-molecular-mass phenolics and double-bond-containing phenolics were produced less. The fraction of aromatic compounds, including benzene, toluene, xylene, and ethylbenzene, was also increased by catalytic reforming. The catalytic effects were more pronounced when the catalyst/biomass ratio was increased. The enhanced production of aromatic compounds by an acidic catalyst obtained in this study is in good agreement with the results of previous studies.

  10. 46 CFR Sec. 10 - Bonds. (United States)


    ... open penalty type. (e) No repair voucher (progress or final) where bond coverage is required shall be... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA...) shall be used. (b) In compliance with the perform- ance bond and payment bond requirements of Article 14...

  11. Direct Mechanism of the First Carbon-Carbon Bond Formation in the Methanol-to-Hydrocarbons Process. (United States)

    Wu, Xinqiang; Xu, Shutao; Zhang, Wenna; Huang, Jindou; Li, Jinzhe; Yu, Bowen; Wei, Yingxu; Liu, Zhongmin


    In the past two decades, the reaction mechanism of C-C bond formation from either methanol or dimethyl ether (DME) in the methanol-to-hydrocarbons (MTH) process has been a highly controversial issue. Described here is the first observation of a surface methyleneoxy analogue, originating from the surface-activated DME, by in situ solid-state NMR spectroscopy, a species crucial to the first C-C bond formation in the MTH process. New insights into the first C-C bond formation were provided, thus suggesting DME/methanol activation and direct C-C bond formation by an interesting synergetic mechanism, involving C-H bond breakage and C-C bond coupling during the initial methanol reaction within the chemical environment of the zeolite catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Molecular heterogeneous catalysts derived from bipyridine-based organosilica nanotubes for C–H bond activation† †Electronic supplementary information (ESI) available: Experimental details, material characterization data, catalytic measurement details. See DOI: 10.1039/c7sc00713b Click here for additional data file. (United States)

    Zhang, Shengbo; Wang, Hua; Li, Mei; Han, Jinyu


    Heterogeneous metal complex catalysts for direct C–H activation with high activity and durability have always been desired for transforming raw materials into feedstock chemicals. This study described the design and synthesis of one-dimensional organosilica nanotubes containing 2,2′-bipyridine (bpy) ligands in the framework (BPy-NT) and their post-synthetic metalation to provide highly active and robust molecular heterogeneous catalysts. By adjusting the ratios of organosilane precursors, very short BPy-NT with ∼50 nm length could be controllably obtained. The post-synthetic metalation of bipyridine-functionalized nanotubes with [IrCp*Cl(μ-Cl)]2 (Cp* = η5-pentamethylcyclopentadienyl) and [Ir(cod)(OMe)]2 (cod = 1,5-cyclooctadiene) afforded solid catalysts, IrCp*-BPy-NT and Ir(cod)-BPy-NT, which were utilized for C–H oxidation of heterocycles and cycloalkanes as well as C–H borylation of arenes. The cut-short nanotube catalysts displayed enhanced activities and durability as compared to the analogous homogeneous catalysts and other conventional heterogeneous catalysts, benefiting from the isolated active sites as well as the fast transport of substrates and products. After the reactions, a detailed characterization of Ir-immobilized BPy-NT via TEM, SEM, nitrogen adsorption, UV/vis, XPS, and 13C CP MAS NMR indicated the molecular nature of the active species as well as stable structures of nanotube scaffolds. This study demonstrates the potential of BPy-NT with a short length as an integration platform for the construction of efficient heterogeneous catalytic systems for organic transformations. PMID:28970878

  13. Plastic-bonded electrodes for nickel-cadmium accumulators. Pt. 8

    Energy Technology Data Exchange (ETDEWEB)

    Mrha, J.; Musilova, M.; Jindra, J.; Polydorova, M.; Peizker, J.; Garche, J.; Hauptmann, M.


    The oxygen recombination (reduction) rate on plastic-bonded cadmium electrodes in sealed Ni-Cd systems can be controlled by the use of a catalytic mix consisting of active carbon and carbon black either in the pure state or mixed with PTFE. This catalytic mix is either rolled onto the gas side of the plastic-bonded cadmium electrode or added to the active material prior to the preparation of the electrode by a rolling technique. The highest oxygen recombination rate, which surpassed that obtained with commercial pocket-type electrodes, was obtained in both cases by the use of an active carbon, carbon black and PTFE catalytic mix. In this case an optimum three-phase boundary, well known from oxygen electrodes for fuel cells, was established.

  14. α-Halogenoacetanilides as hydrogen-bonding organocatalysts that activate carbonyl bonds: fluorine versus chlorine and bromine. (United States)

    Koeller, Sylvain; Thomas, Coralie; Peruch, Fréderic; Deffieux, Alain; Massip, Stéphane; Léger, Jean-Michel; Desvergne, Jean-Pierre; Milet, Anne; Bibal, Brigitte


    α-Halogenoacetanilides (X=F, Cl, Br) were examined as H-bonding organocatalysts designed for the double activation of CO bonds through NH and CH donor groups. Depending on the halide substituents, the double H-bond involved a nonconventional CH⋅⋅⋅O interaction with either a HCXn (n=1-2, X=Cl, Br) or a HCAr bond (X=F), as shown in the solid-state crystal structures and by molecular modeling. In addition, the catalytic properties of α-halogenoacetanilides were evaluated in the ring-opening polymerization of lactide, in the presence of a tertiary amine as cocatalyst. The α-dichloro- and α-dibromoacetanilides containing electron-deficient aromatic groups afforded the most attractive double H-bonding properties towards CO bonds, with a NH⋅⋅⋅O⋅⋅⋅HCX2 interaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Catalytic and substrate promiscuity: distinct multiple chemistries catalysed by the phosphatase domain of receptor protein tyrosine phosphatase. (United States)

    Srinivasan, Bharath; Marks, Hanna; Mitra, Sreyoshi; Smalley, David M; Skolnick, Jeffrey


    The presence of latent activities in enzymes is posited to underlie the natural evolution of new catalytic functions. However, the prevalence and extent of such substrate and catalytic ambiguity in evolved enzymes is difficult to address experimentally given the order-of-magnitude difference in the activities for native and, sometimes, promiscuous substrate/s. Further, such latent functions are of special interest when the activities concerned do not fall into the domain of substrate promiscuity. In the present study, we show a special case of such latent enzyme activity by demonstrating the presence of two mechanistically distinct reactions catalysed by the catalytic domain of receptor protein tyrosine phosphatase isoform δ (PTPRδ). The primary catalytic activity involves the hydrolysis of a phosphomonoester bond (C─O─P) with high catalytic efficiency, whereas the secondary activity is the hydrolysis of a glycosidic bond (C─O─C) with poorer catalytic efficiency. This enzyme also displays substrate promiscuity by hydrolysing diester bonds while being highly discriminative for its monoester substrates. To confirm these activities, we also demonstrated their presence on the catalytic domain of protein tyrosine phosphatase Ω (PTPRΩ), a homologue of PTPRδ. Studies on the rate, metal-ion dependence, pH dependence and inhibition of the respective activities showed that they are markedly different. This is the first study that demonstrates a novel sugar hydrolase and diesterase activity for the phosphatase domain (PD) of PTPRδ and PTPRΩ. This work has significant implications for both understanding the evolution of enzymatic activity and the possible physiological role of this new chemistry. Our findings suggest that the genome might harbour a wealth of such alternative latent enzyme activities in the same protein domain that renders our knowledge of metabolic networks incomplete. © 2016 The Author(s). published by Portland Press Limited on behalf of the

  16. Red/blue shifting hydrogen bonds in acetonitrile-dimethyl sulphoxide solutions: FTIR and theoretical studies (United States)

    Kannan, P. P.; Karthick, N. K.; Mahendraprabu, A.; Shanmugam, R.; Elangovan, A.; Arivazhagan, G.


    FTIR spectra of neat acetonitrile (AN), dimethyl sulphoxide (DMSO) and their binary solutions at various mole fractions have been recorded at room temperature. Theoretical calculations have also been carried out on acetonitrile (monomer, dimer), dimethyl sulphoxide (monomer, dimer) and AN - DMSO complex molecules. 1:2 (AN:DMSO) and 2:1 complexation through the red shifting (AN) C - H ⋯ O = S(DMSO) and blue shifting (DMSO) C - H ⋯ N ≡ C(AN) hydrogen bonds has been identified. The experimental and theoretical studies favour the presence of both the monomer and dimer in liquid AN, but only closed dimers in DMSO. The dipole-dipole interactions existed in AN and DMSO dimers disappear in the complex molecules. Partial π bond between S and O atoms, and three lone pair of electrons on oxygen atom of DMSO have been noticed theoretically.

  17. Electrical and Optical Properties of Si-Incorporated a-C:H Films via the Radio Frequency Plasma-Enhanced Chemical Vapor Deposition Method. (United States)

    Kim, In Jun; Choi, Won Seok; Hong, Byungyou


    The optical and electrical properties of silicon-incorporated hydrogenated amorphous carbon (a-C:H:Si) films deposited via the radio frequency (RF) plasma-enhanced chemical vapor deposition (PECVD) method using a mixture of CH4, H2, and SiH4 were observed. The silane gas whose ranged from 0 to 25 vol.% [SiH4/(SiH4 + CH4) was fed into the reactor while the other deposition parameters were kept constant. The basic properties of these films were investigated via Raman spectroscopy, UV-visible spectrometry, I-V measurement, and surface profiling. The experiment results showed that the film thickness increased from 300 nm to 800 nm for the same deposition time as the silane gas increased. The Raman spectrum obtained from the silicon-incorporated a-C:H films suggested that the film property changed from graphitic-like to more diamond-like. As the silane gas increased, the optical gap, E04, slightly increased from 1.98 eV to 2.62 eV. It was shown that the Si atoms incorporated into the a-C:H films reduced the size of the sp2 clusters. As for the I-V characteristics, the Si-incorporated a-C:H films had a lower leakage current than the a-C:H films without Si.

  18. Molecular catalytic coal liquid conversion

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Yang, Shiyong [Univ. of Chicago, IL (United States)


    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  19. Catalytic Organometallic Reactions of Ammonia (United States)

    Klinkenberg, Jessica L.


    Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity. PMID:20857466

  20. Studies of Catalytic Model Systems

    DEFF Research Database (Denmark)

    Holse, Christian

    of the Cu/ZnO nanoparticles is highly relevant to industrial methanol synthesis for which the direct interaction of Cu and ZnO nanocrystals synergistically boost the catalytic activity. The dynamical behavior of the nanoparticles under reducing and oxidizing environments were studied by means of ex situ X...... as the nanoparticles are reduced. The Cu/ZnO nanoparticles are tested on a  µ-reactor platform and prove to be active towards methanol synthesis, making it an excellent model system for further investigations into activity depended morphology changes....

  1. Catalytic Combustion of Ethyl Acetate


    ÖZÇELİK, Tuğba GÜRMEN; ATALAY, Süheyda; ALPAY, Erden


    The catalytic combustion of ethyl acetate over prepared metal oxide catalysts was investigated. CeO, Co2O3, Mn2O3, Cr2O3, and CeO-Co2O3 catalysts were prepared on monolith supports and they were tested. Before conducting the catalyst experiments, we searched for the homogeneous gas phase combustion reaction of ethyl acetate. According to the homogeneous phase experimental results, 45% of ethyl acetate was converted at the maximum reactor temperature tested (350 °C). All the prepare...

  2. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel


    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  3. Hydrogen bonded supramolecular materials

    CERN Document Server

    Li, Zhan-Ting


    This book is an up-to-date text covering topics in utilizing hydrogen bonding for constructing functional architectures and supramolecular materials. The first chapter addresses the control of photo-induced electron and energy transfer. The second chapter summarizes the formation of nano-porous materials. The following two chapters introduce self-assembled gels, many of which exhibit unique functions. Other chapters cover the advances in supramolecular liquid crystals and the versatility of hydrogen bonding in tuning/improving the properties and performance of materials. This book is designed

  4. Ny arkitektur for nordmenn i Iowa. Arkitekt C.H. Griese, Luther College og kirker i 1860-årene

    Directory of Open Access Journals (Sweden)

    Jens Christian Eldal


    Full Text Available The Norwegian Evangelical-Lutheran Church in America decided in 1861 to build their first college close to the western frontier of The Upper Midwest. The site chosen was a bluff above Upper Iowa River, highly visible from Decorah, a small town founded only 12 years earlier, few years after the first settlers arrived. The college building became a relatively vast structure erected between 1862 and 1865, completed to its originally planned symmetrical composition in 1874. The building style and its composition were common among American colleges and universities further east in the US. It is also demonstrated how the Luther College building façade in composition and detailing shows clear influences from a specific German building. This particular building has been designated as especially typical of the German Rundbogenstil (Style of the Rounded Arch with its great mix of various stylistic elements. The architect was known as C. H. Griese from Cleveland, Ohio. He is identified as Charles Henry Griese (1821–1909, who immigrated from Germany about 1850 and was known as a mason and contractor, from now on also as an architect. In 1869, Griese also designed the three Norwegian Lutheran churches of Washington Prairie, Stavanger and Glenwood in rural Decorah. They represented a Neo Gothic style which was new to the area, and had an evident architectural character contrasting the more ordinary vernacular churches in the area. They signify a change of style and, like the college building, they demonstrate architectural ambitions new to these Norwegians, giving insight also into the general architectural and vernacular development in the area.

  5. Interexaminer reliability in clinical measurement of L*C*h* values of anterior teeth using a spectrophotometer. (United States)

    Hassel, Alexander J; Grossmann, Anne-christiane; Schmitter, Marc; Balke, Zibandeh; Buzello, Anja M


    The objective of this study was to investigate interexaminer reliability in the clinical measurement of the L*C*h* (lightness/value, chroma, hue) values of anterior teeth using a spectrophotometer (Vita Easyshade). The basic color of the maxillary right central incisors and canines of 23 subjects was spectrophotometrically determined by 4 clinicians and an experienced user (development manager) of the spectrophotometer. Also, to analyze the effect of different training with the instrument on interexaminer reliability, 2 of the clinicians were instructed in the use of the spectrophotometer by the experienced examiner, whereas the others instructed themselves by studying the operating manual. Agreement between all examiners was acceptable to excellent (intraclass coefficient > 0.4). The mean value of the measured differences for the central incisors of all subjects for L* values was 5 (for C* = 3.8, h* = 2.7 degrees) and for canines, the mean L* was 4.5 (C* = 3, h* = 1.6 degrees). Results from comparison of the 2 different training methods were inconsistent. Agreement with the experienced examiner ranged from not acceptable (C* values for incisors of self-instructed examiners) to excellent. The distribution of the measurements of 1 subject could lead to deviations in color, probably with clinical impact. For canines, the measurements were at least equally reproducible (in some cases significantly more reproducible) compared to central incisors. Because of the small number of examiners and the inconsistent results, it was not possible to reach a definite conclusion about the effect of different training methods on interexaminer reliability.

  6. The chemical bonds effect of Amaranthus hybridus L. and Dracaena Angustifolia on TiO2 as photo-sensitizer for dye-sensitized solar Cells (DSSC) (United States)

    Ahliha, A. H.; Nurosyid, F.; Supriyanto, A.


    Dye-Sensitized Solar Cells (DSSC) consists of a working electrode, dye, electrolyte, and a counter electrode. The paper showed the effect of chemical bonds Dracaena Angustifolia (suji leaves) and Amaranthus Hybridus L. (spinach leaves) on TiO2 for application in DSSC. Dracaena Angustifolia (suji leaves) and Amaranthus Hybridus L. (spinach leaves) were extracted using acetone solvent as a dye containing chlorophyll, the absorbance spectrum of the dye and TiO2 were characterized using Uv-visible spectrophotometer 1601 PC, the chemical bonds contained in TiO2-dye was characterized using FT-IR spectrophotometer Shimadzu Prestige 21. The efficiency of DSSC was calculated using I-V Keithley 2602A. Absorbance characterization of dye Dracaena Angustifolia showed two peaks at the wavelength of 665,5 nm and 412 nm. The absorbance peaks of dye Amaranthus Hybridus L. at the wavelength of 664 nm and 412,5 nm. FT-IR characterization of TiO2 founded the functional groups C=C-C, C=C-H, C-O, C-H, C=C, C-H aliphatic, and O-H. Dye Amaranthus Hybridus L. obtained functional groups C=C-C, C=C-H, C-O, C-H, C=C, C=O, C-H aliphatic, and O-H. Dye Dracaena Angustifolia obtained functional groups were identified as C=C-C, C=C-H, C-O, C-H, C=C, C-H aliphatic, and O-H. DSSC efficiency with Amaranthus Hybridus L. and Dracaena Angustifolia dyes of 0,063% and 0,058% respectively

  7. Catalytic enantioselective Reformatsky reaction with ketones

    NARCIS (Netherlands)

    Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.


    Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

  8. Catalytic converters in the fireplace

    International Nuclear Information System (INIS)

    Kouki, J.


    In addition to selecting the appropriate means of heating and using dry fuel, the amount of harmful emissions contained by flue gases produced by fireplaces can be reduced by technical means. One such option is to use an oxidising catalytic converter. Tests at TTS Institute's Heating Studies Experimental Station have focused on two such converters (dense and coarse) mounted in light-weight iron heating stoves. The ability of the dense catalytic converter to oxidise carbon monoxide gases proved to be good. The concentration of carbon monoxide in the flue gases was reduced by as much as 90 %. Measurements conducted by VTT (Technical Research Centre of Finland) showed that the conversion of other gases, e.g. of methane, was good. The exhaust resistance caused by the dense converter was so great as to necessitate the mounting of a fluegas evacuation fan in the chimney for the purpose of creating sufficient draught. When relying on natural draught, the dense converter requires a chimney of at least 7 metres and a by-pass connection while the fire is being lit. In addition, the converter will have to be constructed to be less dense and this will mean that it's capability to oxidise non-combusted gases will be reduced. The coarse converter did not impair the draught but it's oxidising property was insufficient. With the tests over, the converter was not observed to have become blocked up by impurities

  9. Adding a new dimension to the investigation of platinum-mediated arene C-H activation reactions using 2D NMR exchange spectroscopy. Dynamics of Pt(II) phenyl/benzene site exchange. (United States)

    Wik, Bror Johan; Lersch, Martin; Krivokapic, Alexander; Tilset, Mats


    Protonation of (N-N)PtPh(2) (1; N-N = diimine ArN=CMe-CMe=NAr with Ar = 2,6-Me(2)C(6)H(3) (a), 2,4,6-Me(3)C(6)H(2) (b), 4-Br-2,6-Me(2)C(6)H(2) (c), 3,5-Me(2)C(6)H(3) (d), and 4-CF(3)C(6)H(4) (e)) in the presence of MeCN at ambient temperature generates (N-N)Pt(Ph)(NCMe)(+) (2). At -78 degrees C, protonation of 1a yielded (N-N)PtPh(2)(H)(NCMe)(+) (3a), which produced benzene and 2a at ca. -40 degrees C. Protonation of 1a-e in CD(2)Cl(2)/Et(2)O-d(10) furnished (N-N)Pt(C(6)H(5))(eta(2)-C(6)H(6))(+) (4a-e). The pi-benzene complexes 4a-c, sterically protected at Pt, eliminate benzene at ca. 0 degree C. The sterically less protected 4d-e lose benzene already at -30 degrees C. SST and 2D EXSY NMR demonstrate that phenyl and pi-benzene ligand protons undergo exchange with concomitant symmetrization of the diimine ligand, most likely via oxidative insertion of Pt into a C-H bond of coordinated benzene. The kinetics of the exchange processes for 4a-c were probed by quantitative EXSY spectroscopy, resulting in DeltaH() of 70-72 kJ mol(-1) and DeltaS of 37-48 J K(-1) mol(-1). A large, strongly temperature-dependent H/D kinetic isotope effect (9.7 at -34 degrees C; 6.9 at -19 degrees C) was measured for the dynamic behavior of 4a versus 4a-d(10), consistent with the proposed pi-benzene C-H bond cleavage. The fact that the pi-benzene complex 4a is thermally more robust in the absence of MeCN than is the Pt(IV) hydridodiphenyl complex 3a in the presence of MeCN agrees with the notion that arene elimination from Pt(IV) hydridoaryl complexes occurs via Pt(II) pi-arene intermediates that eliminate the hydrocarbon associatively, in this case, promoted by MeCN. Compounds 1a, 1b, 1d, 2a, and 2b have been crystallographically characterized.

  10. Cytotoxicity of dentin bonding agents. (United States)

    Cal, Ebru; Guneri, Pelin; Atay, Ayse; Cetintas, Vildan Bozok


    This study sought to evaluate the cytotoxicity of 5 dentin bonding agents (Admira Bond, Adper Single Bond Plus, Clearfil SE Bond, Clearfil S3 Bond, and Heliobond) by XTT assay using human gingival fibroblast cells. Samples of dentin bonding agents were prepared on a black 96-well microplate, and the cytotoxicity of each bonding material was measured every 24 hours for 7 days, then on Days 14, 21, and 28. One-way ANOVA and Bonferroni post hoc tests were used for statistical analyses. All 5 materials were evaluated as severely cytotoxic (P agents showed severe cytotoxicity with viability results exception of Adper Single Bond Plus, toxicity continued to Day 28 for all compounds. The utmost care must be considered during the clinical utilization of dentin bonding agents to keep them within the area of restoration and prevent their contact with adjacent tissues.

  11. Photochemical tissue bonding (United States)

    Redmond, Robert W [Brookline, MA; Kochevar, Irene E [Charlestown, MA


    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  12. C-H Acetoxylation-Based Chemical Synthesis of 17 β-Hydroxymethyl-17 α-methyl-18-norandrost-13-ene Steroids. (United States)

    Hurski, Alaksiej L; Barysevich, Maryia V; Dalidovich, Tatsiana S; Iskryk, Marharyta V; Kolasava, Nastassia U; Zhabinskii, Vladimir N; Khripach, Vladimir A


    Palladium-catalyzed C-H acetoxylation has been proposed as a key transformation in the first chemical synthesis of steroids bearing a unique 17β-hydroxymethyl-17α-methyl-18-nor-13-ene D-fragment. This C-H functionalization step was crucial for inverting the configuration at the quaternary stereocenter of a readily available synthetic intermediate. The developed approach was applied to prepare the metandienone metabolite needed as a reference substance in anti-doping analysis to control the abuse of this androgenic anabolic steroid. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Rapid access to the core skeleton of the [3 + 2]-type dimeric pyrrole-imidazole alkaloids by triplet ketone-mediated C-H functionalization. (United States)

    You, Lin; Chen, Chuo


    The ability of triplet ketones to abstract a hydrogen atom from hydrocarbons is reminiscent of that of the high-spin metal-oxo complexes in C-H oxidation enzymes. In practice, the reactivity of triplet ketones is easier to control and applicable to promoting a wider range of reactions. We demonstrate herein the synthetic utility of triplet ketone-mediated C -addition of methanol to cyclopentenone derivatives with an expedient synthesis of the core skeleton of the [3+2]-type dimeric pyrrole-imidazole alkaloids. Remarkably, this photochemical C-H functionalization reaction is highly regioselective and can tolerate a good range of functional groups.

  14. Local atomic structure and chemical order in amorphous SiGe:H and SiC:H alloys

    International Nuclear Information System (INIS)

    Pisarkiewicz, T.; Stapinski, T.


    The local structure and chemical ordering in amorphous hydrogenated silicon-germanium and silicon-carbon alloys were analyzed mainly with the help of extended x-ray absorption fine structure (EXAFS) spectroscopy, Raman scattering and electron diffraction. Ge-Ge and Ge-Si distances were found to be independent of concentration and the composition of the first coordination shell around Ge is consistent with a random mixing of the two species in a-Si 1-x Ge:H alloy. The first-coordination-shell average bond lengths for Si-Si and SiC in a-Si 1-x C x :H are also constant with concentration x and the comparison of the first coordination shell composition around Si with average concentration indicates that the alloys tends to be chemically ordered. The degree of crystallinity in microcrystalline Si films determined by EXAFS is in agreement with that obtained in Raman scattering analysis. (author). 16 refs, 5 figs

  15. Catalytic arylation methods from the academic lab to industrial processes

    CERN Document Server

    Burke, Anthony J


    This "hands-on" approach to the topic of arylation consolidates the body of key research over the last ten years (and up to around 2014) on various catalytic methods which involve an arylation process. Clearly structured, the chapters in this one-stop resource are arranged according to the reaction type, and focus on novel, efficient and sustainable processes, rather than the well-known and established cross-coupling methods. The entire contents are written by two authors with academic and industrial expertise to ensure consistent coverage of the latest developments in the field, as well as industrial applications, such as C-H activation, iron and gold-catalyzed coupling reactions, cycloadditions or novel methodologies using arylboron reagents. A cross-section of relevant tried-and-tested experimental protocols is included at the end of each chapter for putting into immediate practice, along with patent literature. Due to its emphasis on efficient, "green" methods and industrial applications of the products c...

  16. Fabrication of fuel cell electrodes and other catalytic structures (United States)

    Smith, J.L.


    A porous layer of catalyst material suitable for use as an electrode in a molten carbonate fuel cell includes elongated pores substantially extending across the layer thickness. The catalyst layer is prepared by depositing particulate catalyst material into polymeric flocking on a substrate surface by a procedure such as tape casting. The loaded substrate is heated in a series of steps with rising temperatures to set the tape, thermally decompose the substrate with flocking and sinter bond the catalyst particles into a porous catalytic layer with elongated pores across its thickness. Employed as an electrode, the elongated pores provide distribution of reactant gas into contact with catalyst particles wetted by molten electrolyte. 1 fig.

  17. Catalytic ring opening of decalin. Biofunctional versus hydrogenolytic pathways

    Energy Technology Data Exchange (ETDEWEB)

    Weitkamp, J.; Rabl, S.; Haas, A.; Santi, D. [Stuttgart Univ. (Germany). Inst. of Chemical Technology; Ferrari, M.; Calemma, V. [Eni R and M Div., San Donato Milanese (Italy)


    Ir/silica, Pt/La-X and Rh/H-Beta were prepared and tested in the hydroconversion of cisdecalin at different temperatures. The catalytic tests were carried out under hydrogen in a high-pressure flow-type apparatus at 5.2 MPa. On the three catalysts open-chain decane yields up to 20 % were achieved, which is much higher than the yields reported so far in the literature. Pt/La-X and Rh/H-Beta behave as bifunctional catalysts with a high tendency for skeletal isomerization. On these catalysts the so-called paring reaction via carbenium ions occurs, leading to iso-butane and methylcyclopentane as main hydrocracked products. On Ir/SiO{sub 2}, carbon-carbon bond cleavage occurs through hydrogenolysis on the noble metal without prior isomerization. As a consequence the product spectrum is less complex than on the bifunctional catalysts which makes the system particularly amenable to mechanistic studies. (orig.)

  18. Improving selectivity in catalytic hydrodefluorination by limiting SNV reactivity. (United States)

    Krüger, Juliane; Ehm, Christian; Lentz, Dieter


    Catalytic hydrodefluorination of perfluoroallylbenzene with Cp 2 TiH in THF is unselective and yields a variety of previously unknown compounds, predominantly activated in the allylic position. Several different mechanisms have been examined in detail using solvent corrected (THF) DFT(M06-2X) calculations for the archetypal perfluorinated olefin perfluoropropene and perfluoroallylbenzene: (a) single electron transfer, (b) hydrometallation/fluoride elimination, (c) σ-bond metathesis (allylic or vinylic), and (d) nucleophilic vinylic substitution (S N V, w/o Ti-F contacts in the TS). S N V is shown to be a competitive mechanism to hydrometallation and proceeds via ionic species from which F-elimination is facile and unselective leading to low selectivity in polar solvents. Subsequent experiments show that selectivity can be increased in a non-polar solvent.

  19. Comparison of shear bond strength of the stainless steel metallic brackets bonded by three bonding systems

    Directory of Open Access Journals (Sweden)

    Mehdi Ravadgar


    Full Text Available Introduction: In orthodontic treatment, it is essential to establish a satisfactory bond between enamel and bracket. After the self-etch primers (SEPs were introduced for the facilitation of bracket bonding in comparison to the conventional etch-and-bond system, multiple studies have been carried out on their shear bond strengths which have yielded different results. This study was aimed at comparing shear bond strengths of the stainless steel metallic brackets bonded by three bonding systems. Methods: In this experimental in vitro study, 60 extracted human maxillary premolar teeth were randomly divided into three equal groups: in the first group, Transbond XT (TBXT light cured composite was bonded with Transbond plus self-etching primer (TPSEP; in the second group, TBXT composite was bonded with the conventional method of acid etching; and in the third group, the self cured composite Unite TM bonding adhesive was bonded with the conventional method of acid etching. In all the groups, Standard edgewise-022 metallic brackets (American Orthodontics, Sheboygan, USA were used. Twenty-four hours after the completion of thermocycling, shear bond strength of brackets was measured by Universal Testing Machine (Zwick. In order to compare the shear bond strengths of the groups, the variance analysis test (ANOVA was adopted and p≤0.05 was considered as a significant level. Results: Based on megapascal, the average shear bond strength for the first, second, and third groups was 8.27±1.9, 9.78±2, and 8.92±2.5, respectively. There was no significant difference in the shear bond strength of the groups. Conclusions: Since TPSEP shear bond strength is approximately at the level of the conventional method of acid etching and within the desirable range for orthodontic brackets shear bond strength, applying TPSEP can serve as a substitute for the conventional method of etch and bond, particularly in orthodontic operations.

  20. Fluorogenic, catalytic, photochemical reaction for amplified detection of nucleic acids. (United States)

    Dutta, Subrata; Fülöp, Annabelle; Mokhir, Andriy


    Photochemical, nucleic acid-induced reactions, which are controlled by nontoxic red light, are well-suited for detection of nucleic acids in live cells, since they do not require any additives and can be spatially and temporally regulated. We have recently described the first reaction of this type, in which a phenylselenyl derivative of thymidine (5'-PhSeT-ODNa) is cleaved in the presence of singlet oxygen (Fülöp, A., Peng, X., Greenberg, M. M., Mokhir, A. (2010) A nucleic acid directed, red light-induced chemical reaction. Chem. Commun. 46, 5659-5661). The latter reagent is produced upon exposure of a photosensitizer 3'-PS-ODNb (PS = Indium(III)-pyropheophorbide-a-chloride: InPPa) to >630 nm light. In 2012 we reported on a fluorogenic version of this reaction (Dutta, S., Flottmann, B., Heilemann, M., Mokhir, A. (2012) Hybridization and reaction-based, fluorogenic nucleic acid probes. Chem. Commun. 47, 9664-9666), which is potentially applicable for the detection of nucleic acids in cells. Unfortunately, its yield does not exceed 25% and no catalytic turnover could be observed in the presence of substrate excess. This problem occurs due to the efficient, competing oxidation of the substrate containing an electron rich carbon-carbon double bonds (SCH═CHS) in the presence of singlet oxygen with formation of a noncleavable product (SCH═CHSO). Herein we describe a related, but substantially improved photochemical, catalytic transformation of a fluorogenic, organic substrate, which consists of 9,10-dialkoxyanthracene linked to fluorescein, with formation of a bright fluorescent dye. In highly dilute solution this reaction occurs only in the presence of a nucleic acid template. We developed three types of such a reaction and demonstrated that they are high yielding and generate over 7.7 catalytic turnovers, are sensitive to single mismatches in nucleic acid targets, and can be applied for determination of both the amount of nucleic acids and potentially their