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

Science.gov (United States)

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

2014-09-14

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.

Short hydrogen bonds in the catalytic mechanism of serine proteases

Directory of Open Access Journals (Sweden)

VLADIMIR LESKOVAC

2008-04-01

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.

A bonding study of c-C5H8 adsorption on Pt(111)

International Nuclear Information System (INIS)

Simonetti, S.; Jasen, P.; Gonzalez, E.; Juan, A.; Brizuela, G.

2006-01-01

The chemisorption of cyclopentane (c-C 5 H 8 ) on Pt(111) has been studied using a qualitative band-structure calculations in the framework of tight-binding implementation with the YAeHMOP package. We modeled the metal surface by a two-dimensional slab of finite thickness with an overlayer of c-C 5 H 8 , in a (3x3) di-σ geometry. The c-C 5 H 8 molecule is attached to the surface with its C?C atoms bonded mainly with two Pt atoms while the opposite CH 2 bends towards the surface. The Pt?Pt bonds in the underlying surface and the C?C bonds of c-C 5 H 8 are weakened upon the chemisorption. A noticeable Pt-H and Pt-C interactions has been observed. We found that of Pt 5d z 2 band plays an important role in the bonding between c-C 5 H 8 and the surface, as do the Pt 6s and 6p z bands. The HOMO-LUMO bands of c-C 5 H 8 are very dispersed, indicative of a strong interaction with the metal surface

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

Science.gov (United States)

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alkane Activation at Ambient Temperatures: Unusual Selectivities, C-C, C-H Bond Scission versus C-C Bond Coupling

NARCIS (Netherlands)

Trionfetti, C.; Agiral, A.; Gardeniers, Johannes G.E.; Lefferts, Leonardus; Seshan, Kulathuiyer

2008-01-01

Activating bonds: A cold plasma generated by dielectric barrier discharge in a microreactor converts alkanes (C1–C3) at atmospheric pressure. Large amounts of products with higher molecular weight than the starting hydrocarbons are observed showing that C-H activation at lower T favourably leads to

Multiple C-H Bond Activations and Ring-Opening C-S Bond Cleavage of Thiophene by Dirhenium Carbonyl Complexes.

Science.gov (United States)

Adams, Richard D; Dhull, Poonam; Tedder, Jonathan D

2018-06-14

The reaction of Re 2 (CO) 8 (μ-C 6 H 5 )(μ-H) (1) with thiophene in CH 2 Cl 2 at 40 °C yielded the new compound Re 2 (CO) 8 (μ-η 2 -SC 4 H 3 )(μ-H) (2), which contains a bridging σ-π-coordinated thienyl ligand formed by the activation of the C-H bond at the 2 position of the thiophene. Compound 2 exhibits dynamical activity on the NMR time scale involving rearrangements of the bridging thienyl ligand. The reaction of compound 2 with a second 1 equiv of 1 at 45 °C yielded the doubly metalated product [Re 2 (CO) 8 (μ-H)] 2 (μ-η 2 -2,3-μ-η 2 -4,5-C 4 H 2 S) (3), formed by the activation of the C-H bond at the 5 position of the thienyl ligand in 2. Heating 3 in a hexane solvent to reflux transformed it into the ring-opened compound Re(CO) 4 [μ-η 5 -η 2 -SCC(H)C(H)C(H)][Re(CO) 3 ][Re 2 (CO) 8 (μ-H)] (4) by the loss of one CO ligand. Compound 4 contains a doubly metalated 1-thiapentadienyl ligand formed by the cleavage of one of the C-S bonds. When heated to reflux (125 °C) in an octane solvent in the presence of H 2 O, the new compound Re(CO) 4 [η 5 -μ-η 2 -SC(H)C(H)C(H)C(H)]Re(CO) 3 (5) was obtained by cleavage of the Re 2 (CO) 8 (μ-H) group from 4 with formation of the known coproduct [Re(CO) 3 (μ 3 -OH)] 4 . All new products were characterized by single-crystal X-ray diffraction analyses.

Mo-Mo Quintuple Bond is Highly Reactive in H-H, C-H, and O-H σ-Bond Cleavages Because of the Polarized Electronic Structure in Transition State.

Science.gov (United States)

Chen, Yue; Sakaki, Shigeyoshi

2017-04-03

The recently reported high reactivity of the Mo-Mo quintuple bond of Mo 2 (N ∧ N) 2 (1) {N ∧ N = μ-κ 2 -CH[N(2,6-iPr 2 C 6 H 3 )] 2 } in the H-H σ-bond cleavage was investigated. DFT calculations disclosed that the H-H σ-bond cleavage by 1 occurs with nearly no barrier to afford the cis-dihydride species followed by cis-trans isomerization to form the trans-dihydride product, which is consistent with the experimental result. The O-H and C-H bond cleavages by 1 were computationally predicted to occur with moderate (ΔG° ⧧ = 9.0 kcal/mol) and acceptable activation energies (ΔG° ⧧ = 22.5 kcal/mol), respectively, suggesting that the Mo-Mo quintuple bond can be applied to various σ-bond cleavages. In these σ-bond cleavage reactions, the charge-transfer (CT Mo→XH ) from the Mo-Mo quintuple bond to the X-H (X = H, C, or O) bond and that (CT XH→Mo ) from the X-H bond to the Mo-Mo bond play crucial roles. Though the HOMO (dδ-MO) of 1 is at lower energy and the LUMO + 2 (dδ*-MO) of 1 is at higher energy than those of RhCl(PMe 3 ) 2 (LUMO and LUMO + 1 of 1 are not frontier MO), the H-H σ-bond cleavage by 1 more easily occurs than that by the Rh complex. Hence, the frontier MO energies are not the reason for the high reactivity of 1. The high reactivity of 1 arises from the polarization of dδ-type MOs of the Mo-Mo quintuple bond in the transition state. Such a polarized electronic structure enhances the bonding overlap between the dδ-MO of the Mo-Mo bond and the σ*-antibonding MO of the X-H bond to facilitate the CT Mo→XH and reduce the exchange repulsion between the Mo-Mo bond and the X-H bond. This polarized electronic structure of the transition state is similar to that of a frustrated Lewis pair. The easy polarization of the dδ-type MOs is one of the advantages of the metal-metal multiple bond, because such polarization is impossible in the mononuclear metal complex.

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

Energy Technology Data Exchange (ETDEWEB)

Lewis, Jared; Bergman, Robert; Ellman, Jonathan

2008-02-04

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

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

Science.gov (United States)

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

2014-10-09

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.

Direct approaches to nitriles via highly efficient nitrogenation strategy through C-H or C-C bond cleavage.

Science.gov (United States)

Wang, Teng; Jiao, Ning

2014-04-15

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

Reactive carbon-chain molecules: synthesis of 1-diazo-2,4-pentadiyne and spectroscopic characterization of triplet pentadiynylidene (H-C[triple bond]C-:C-C[triple bond]C-H).

Science.gov (United States)

Bowling, Nathan P; Halter, Robert J; Hodges, Jonathan A; Seburg, Randal A; Thomas, Phillip S; Simmons, Christopher S; Stanton, John F; McMahon, Robert J

2006-03-15

1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C[triple bond]C-:C-C[triple bond]C-H). Theory predicts an axially symmetric (D(infinity h)) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (absolute value(D/hc) = 0.6157 cm(-1), absolute value(E/hc) = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O2-doped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.

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

Science.gov (United States)

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

2015-11-01

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.

A novel disulfide bond in the SH2 Domain of the C-terminal Src kinase controls catalytic activity.

Science.gov (United States)

Mills, Jamie E; Whitford, Paul C; Shaffer, Jennifer; Onuchic, Jose N; Adams, Joseph A; Jennings, Patricia A

2007-02-02

The SH2 domain of the C-terminal Src kinase [Csk] contains a unique disulfide bond that is not present in other known SH2 domains. To investigate whether this unusual disulfide bond serves a novel function, the effects of disulfide bond formation on catalytic activity of the full-length protein and on the structure of the SH2 domain were investigated. The kinase activity of full-length Csk decreases by an order of magnitude upon formation of the disulfide bond in the distal SH2 domain. NMR spectra of the fully oxidized and fully reduced SH2 domains exhibit similar chemical shift patterns and are indicative of similar, well-defined tertiary structures. The solvent-accessible disulfide bond in the isolated SH2 domain is highly stable and far from the small lobe of the kinase domain. However, reduction of this bond results in chemical shift changes of resonances that map to a cluster of residues that extend from the disulfide bond across the molecule to a surface that is in direct contact with the small lobe of the kinase domain in the intact molecule. Normal mode analyses and molecular dynamics calculations suggest that disulfide bond formation has large effects on residues within the kinase domain, most notably within the active-site cleft. Overall, the data indicate that reversible cross-linking of two cysteine residues in the SH2 domain greatly impacts catalytic function and interdomain communication in Csk.

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

Directory of Open Access Journals (Sweden)

Yong Liang

2015-03-01

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.

Studies on the selectivity of the reaction of (CO){sub 5}W=C(aryl)H with enynes: transfer of the carbene ligand to the C=C Bond versus insertion of the C triple bond C into the W=C Bond

Energy Technology Data Exchange (ETDEWEB)

Fischer, H.; Volkland, H.P.; Stumpf, R.

1996-10-01

The strongly electrophilic monophenylcarbene complex [(CO){sub 5}W=C(Ph)H] (2a) reacts with the enynes H-C triple bond C-R(R=-C(Me)=CH{sub 2})(3), -C{sub 6}H{sub 4}-CH=CH{sub 2}-p (5) and subsequently with PMe{sub 3} to form the C{sub a}lpha-PMe{sub 3} adducts of the vinylidene complexes [(CO){sub 5}W-{l_brace}C(PMe{sub 3})=CH-C{sub 3}H{sub 3}(Me)Ph{r_brace}] (4) and [(CO){sub 5}W {l_brace}C(PMe{sub 3})=CH-C{sub 6}H{sub 4}-C{sub 3}H{sub 4}Ph{r_brace}] (6). The reaction very likely proceeds by transfer of the carbene ligand to the C=C bond of the enyne to form a cyclopropyl-substituted alkyne complex which is in equilibrium with its vinylidene isomer.

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

Science.gov (United States)

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

2017-07-26

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

Phenylacetylene and H bond

Indian Academy of Sciences (India)

... all resembling H bonds. Non-linear H bonds due to secondary interactions. C-H stretching frequency shows blue shift. Heavy atom distances are longer than the sum of van der Waals radii. Formed a task group through IUPAC to come up with a modern definition of H bond. 15 international experts including Desiraju.

Oxidative addition of C--H bonds in organic molecules to transition metal centers

International Nuclear Information System (INIS)

Bergman, R.G.

1989-04-01

Alkanes are among the most chemically inert organic molecules. They are reactive toward a limited range of reagents, such as highly energetic free radicals and strongly electrophilic and oxidizing species. This low reactivity is a consequence of the C--H bond energies in most saturated hydrocarbons. These values range from 90 to 98 kcal/mole for primary and secondary C--H bonds; in methane, the main constituent of natural gas, the C--H bond energy is 104 kcal/mole. This makes methane one of the most common but least reactive organic molecules in nature. This report briefly discusses the search for metal complexes capable of undergoing the C--H oxidative addition process allowing alkane chemistry to be more selective than that available using free radical reagents. 14 refs

Catalyst-Dependent Chemoselective Formal Insertion of Diazo Compounds into C-C or C-H Bonds of 1,3-Dicarbonyl Compounds.

Science.gov (United States)

Liu, Zhaohong; Sivaguru, Paramasivam; Zanoni, Giuseppe; Anderson, Edward A; Bi, Xihe

2018-05-08

A catalyst-dependent chemoselective one-carbon insertion of diazo compounds into the C-C or C-H bonds of 1,3-dicarbonyl species is reported. In the presence of silver(I) triflate, diazo insertion into the C(=O)-C bond of the 1,3-dicarbonyl substrate leads to a 1,4-dicarbonyl product containing an all-carbon α-quaternary center. This reaction constitutes the first example of an insertion of diazo-derived carbenoids into acyclic C-C bonds. When instead scandium(III) triflate was applied as the catalyst, the reaction pathway switched to formal C-H insertion, affording 2-alkylated 1,3-dicarbonyl products. Different reaction pathways are proposed to account for this powerful catalyst-dependent chemoselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium-Catalyzed ortho C-H Arylation of Benzaldehydes Using ortho-Sulfinyl Aniline Transient Auxiliary.

Science.gov (United States)

Mu, Delong; He, Gang; Chen, Gong

2018-05-03

A PdII-catalyzed ortho-(Csp2)-H arylation reaction of benzaldehydes using catalytic amount of 2-methylsulfinyl-aniline as transient auxiliary was developed. This reaction is compatible with a broad range of benzaldehyde and aryl iodide substrates. Compared with other related reaction systems, an excellent regioselectivity for ortho-C(sp2)-H bonds over benzylic C(sp3)-H bonds was obtained for ortho-alkyl-benzaldehyde substrates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox-neutral rhodium-catalyzed C-H functionalization of arylamine N-oxides with diazo compounds: primary C(sp(3))-H/C(sp(2))-H activation and oxygen-atom transfer.

Science.gov (United States)

Zhou, Bing; Chen, Zhaoqiang; Yang, Yaxi; Ai, Wen; Tang, Huanyu; Wu, Yunxiang; Zhu, Weiliang; Li, Yuanchao

2015-10-05

An unprecedented rhodium(III)-catalyzed regioselective redox-neutral annulation reaction of 1-naphthylamine N-oxides with diazo compounds was developed to afford various biologically important 1H-benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by-products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp(3) )H bond and C(sp(2) )H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)-catalyzed coupling of readily available tertiary aniline N-oxides with α-diazomalonates was also developed under external oxidant-free conditions to access various aminomandelic acid derivatives by an O-atom-transfer reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A meta-selective C-H borylation directed by a secondary interaction between ligand and substrate

Science.gov (United States)

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

2015-09-01

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.

Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate.

Science.gov (United States)

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

2015-01-28

(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.

Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions.

Science.gov (United States)

Corbin, Joshua R; Schomaker, Jennifer M

2017-04-13

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.

Catalytic routes to fuels from C1 and oxygenate molecules

KAUST Repository

Wang, Shuai

2017-02-23

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

Catalytic routes to fuels from C1 and oxygenate molecules

KAUST Repository

Wang, Shuai; Agirrezabal-Telleria, Iker; Bhan, Aditya; Simonetti, Dante; Takanabe, Kazuhiro; Iglesia, Enrique

2017-01-01

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

The role of uranium-arene bonding in H2O reduction catalysis

Science.gov (United States)

Halter, Dominik P.; Heinemann, Frank W.; Maron, Laurent; Meyer, Karsten

2018-03-01

The reactivity of uranium compounds towards small molecules typically occurs through stoichiometric rather than catalytic processes. Examples of uranium catalysts reacting with water are particularly scarce, because stable uranyl groups form that preclude the recovery of the uranium compound. Recently, however, an arene-anchored, electron-rich uranium complex has been shown to facilitate the electrocatalytic formation of H2 from H2O. Here, we present the precise role of uranium-arene δ bonding in intermediates of the catalytic cycle, as well as details of the atypical two-electron oxidative addition of H2O to the trivalent uranium catalyst. Both aspects were explored by synthesizing mid- and high-valent uranium-oxo intermediates and by performing comparative studies with a structurally related complex that cannot engage in δ bonding. The redox activity of the arene anchor and a covalent δ-bonding interaction with the uranium ion during H2 formation were supported by density functional theory analysis. Detailed insight into this catalytic system may inspire the design of ligands for new uranium catalysts.

Clean and Selective Catalytic C-H alkylation of Alkenes with Environmental friendly Alcohols

KAUST Repository

Poater, Albert

2016-09-14

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.

c-C5H5 on a Ni(1 1 1) surface: Theoretical study of the adsorption, electronic structure and bonding

International Nuclear Information System (INIS)

German, E.; Simonetti, S.; Pronsato, E.; Juan, A.; Brizuela, G.

2008-01-01

In the present work the ASED-MO method is applied to study the adsorption of cyclopentadienyl anion on a Ni(1 1 1) surface. The adsorption with the centre of the aromatic ring placed above the hollow position has been identified to be energetically the most favourable. The aromatic ring remains almost flat, the H atoms are tilted 17 deg. away from the metal surface. We modelled the metal surface by a two-dimensional slab of finite thickness, with an overlayer of c-C 5 H 5 - , one c-C 5 H 5 - per nine surface Ni atoms. The c-C 5 H 5 - molecule is attached to the surface with its five C atoms bonding mainly with three Ni atoms. The Ni-Ni bond in the underlying surface and the C-C bonds of c-C 5 H 5 - are weakened upon adsorption. We found that the band of Ni 5d z 2 orbitals plays an important role in the bonding between c-C 5 H 5 - and the surface, as do the Ni 6s and 6p z bands

Correlation between catalytic activity and bonding and coordination number of atoms and molecules on transition metal surfaces: theory and experimental evidence

International Nuclear Information System (INIS)

Falicov, L.M.; Somorjai, G.A.

1985-01-01

Correlation between catalytic activity and low-energy local electronic fluctuation in transition metals is proposed. A theory and calculations are presented which indicate that maximum electronic fluctuants take place at high-coordination metal sites. Either (i) atomically rough surfaces that expose to the reactant molecules atoms with large numbers of nonmagnetic or weakly magnetic neighbors in the first or second layer at the surface or (ii) stepped and kinked surfaces are the most active in carrying out structure-sensitive catalytic reactions. The synthesis of ammonia from N 2 and H 2 over iron and rhenium surfaces, 1 H 2 / 2 H 2 exchange over stepped platinum crystal surfaces at low pressures, and the hydrogenolysis (C - C bond breaking) of isobutane at kinked platinum crystal surfaces are presented as experimental evidence in support of the theory

Selective sp3 C-H alkylation via polarity-match-based cross-coupling.

Science.gov (United States)

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

2017-07-06

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.

Selective sp3 C-H alkylation via polarity-match-based cross-coupling

Science.gov (United States)

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

2017-07-01

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.

Photoelectron Diffraction Imaging for C2H2 and C2H4 Chemisorbed on Si(100) Reveals a New Bonding Configuration

International Nuclear Information System (INIS)

Xu, S. H.; Keeffe, M.; Yang, Y.; Chen, C.; Yu, M.; Lapeyre, G. J.; Rotenberg, E.; Denlinger, J.; Yates, J. T. Jr.

2000-01-01

A new adsorption site for adsorbed acetylene on Si(100) is observed by photoelectron imaging based on the holographic principle. The diffraction effects in the carbon 1s angle-resolved photoemission are inverted (including the small-cone method) to obtain an image of the atom's neighboring carbon. The chemisorbed acetylene molecule is bonded to four silicon surface atoms. In contrast to the C 2 H 2 case, the image for adsorbed C 2 H 4 shows it bonded to two Si surface atoms. (c) 2000 The American Physical Society

Recent advances in C(sp3–H bond functionalization via metal–carbene insertions

Directory of Open Access Journals (Sweden)

Bo Wang

2016-04-01

Full Text Available The recent development of intermolecular C–H insertion in the application of C(sp3–H bond functionalizations, especially for light alkanes, is reviewed. The challenging problem of regioselectivity in C–H bond insertions has been tackled by the use of sterically bulky metal catalysts, such as metal porphyrins and silver(I complexes. In some cases, high regioselectivity and enantioselectivity have been achieved in the C–H bond insertion of small alkanes. This review highlights the most recent accomplishments in this field.

C=C bond cleavage on neutral VO3(V2O5)n clusters.

Science.gov (United States)

Dong, Feng; Heinbuch, Scott; Xie, Yan; Bernstein, Elliot R; Rocca, Jorge J; Wang, Zhe-Chen; Ding, Xun-Lei; He, Sheng-Gui

2009-01-28

The reactions of neutral vanadium oxide clusters with alkenes (ethylene, propylene, 1-butene, and 1,3-butadiene) are investigated by experiments and density function theory (DFT) calculations. Single photon ionization through extreme ultraviolet radiation (EUV, 46.9 nm, 26.5 eV) is used to detect neutral cluster distributions and reaction products. In the experiments, we observe products (V(2)O(5))(n)VO(2)CH(2), (V(2)O(5))(n)VO(2)C(2)H(4), (V(2)O(5))(n)VO(2)C(3)H(4), and (V(2)O(5))(n)VO(2)C(3)H(6), for neural V(m)O(n) clusters in reactions with C(2)H(4), C(3)H(6), C(4)H(6), and C(4)H(8), respectively. The observation of these products indicates that the C=C bonds of alkenes can be broken on neutral oxygen rich vanadium oxide clusters with the general structure VO(3)(V(2)O(5))(n=0,1,2...). DFT calculations demonstrate that the reaction VO(3) + C(3)H(6) --> VO(2)C(2)H(4) + H(2)CO is thermodynamically favorable and overall barrierless at room temperature. They also provide a mechanistic explanation for the general reaction in which the C=C double bond of alkenes is broken on VO(3)(V(2)O(5))(n=0,1,2...) clusters. A catalytic cycle for alkene oxidation on vanadium oxide is suggested based on our experimental and theoretical investigations. The reactions of V(m)O(n) with C(6)H(6) and C(2)F(4) are also investigated by experiments. The products VO(2)(V(2)O(5))(n)C(6)H(4) are observed for dehydration reactions between V(m)O(n) clusters and C(6)H(6). No product is detected for V(m)O(n) clusters reacting with C(2)F(4). The mechanisms of the reactions between VO(3) and C(2)F(4)/C(6)H(6) are also investigated by calculations at the B3LYP/TZVP level.

Mechanistic Insights on C-O and C-C Bond Activation and Hydrogen Insertion during Acetic Acid Hydrogenation Catalyzed by Ruthenium Clusters in Aqueous Medium

Energy Technology Data Exchange (ETDEWEB)

Shangguan, Junnan; Olarte, Mariefel V.; Chin, Ya-Huei [Cathy

2016-06-07

Catalytic pathways for acetic acid (CH3COOH) and hydrogen (H2) reactions on dispersed Ru clusters in the aqueous medium and the associated kinetic requirements for C-O and C-C bond cleavages and hydrogen insertion are established from rate and isotopic assessments. CH3COOH reacts with H2 in steps that either retain its carbon backbone and lead to ethanol, ethyl acetate, and ethane (47-95 %, 1-23 %, and 2-17 % carbon selectivities, respectively) or break its C-C bond and form methane (1-43 % carbon selectivities) at moderate temperatures (413-523 K) and H2 pressures (10-60 bar, 298 K). Initial CH3COOH activation is the kinetically relevant step, during which CH3C(O)-OH bond cleaves on a metal site pair at Ru cluster surfaces nearly saturated with adsorbed hydroxyl (OH*) and acetate (CH3COO*) intermediates, forming an adsorbed acetyl (CH3CO*) and hydroxyl (OH*) species. Acetic acid turnover rates increase proportionally with both H2 (10-60 bar) and CH3COOH concentrations at low CH3COOH concentrations (<0.83 M), but decrease from first to zero order as the CH3COOH concentration and the CH3COO* coverages increase and the vacant Ru sites concomitantly decrease. Beyond the initial CH3C(O)-OH bond activation, sequential H-insertions on the surface acetyl species (CH3CO*) lead to C2 products and their derivative (ethanol, ethane, and ethyl acetate) and the competitive C-C bond cleavage of CH3CO* causes the eventual methane formation. The instantaneous carbon selectivities towards C2 species (ethanol, ethane, and ethyl acetate) increase linearly with the concentration of proton-type Hδ+ (derived from carboxylic acid dissociation) and chemisorbed H*. The selectivities towards C2 products decrease with increasing temperature, because of higher observed barriers for C-C bond cleavage than H-insertion. This study offers an interpretation of mechanism and energetics and provides kinetic evidence of carboxylic acid assisted proton-type hydrogen (Hδ+) shuffling during H

Gas-phase reactivity of lanthanide cations with fluorocarbons: C-F versus C-H and C-C bond activation

International Nuclear Information System (INIS)

Cornehl, H.H.; Hornung, G.; Schwarz, H.

1996-01-01

The gas-phase reactivity of the fluorinated hydrocarbons CF 4 , CHF 3 , CH 3 F, C 2 F 6 , 1,1-C 2 H 4 F 2 , and C 6 F 6 with the lanthanide cations Ce + , Pr + , Sm + , Ho + , Tm + , and Yb + and the reactivity of C 6 H 5 F with all lanthanide cations Ln + (Ln = La-Lu, with the exception of Pm + ) have been examined by Fourier-transform ion cyclotron resonance mass spectrometry. The perfluorinated compounds tetrafluoromethane and hexafluoroethane as well as trifluoromethane do not react with any lanthanide cation. Selective activation of the strong C-F bonds in fluoromethane, 1,1-difluoroethane, hexafluorobenzene, and fluorobenzene appears as a general reaction scheme along the 4f row. Experimental evidence is given for a 'harpoon'-like mechanism for the F atom abstraction process which operates via an initial electron transfer from the lanthanide cation to the fluorinated substrate in the encounter complex Ln + RF. The most reactive lanthanides La + , Ce + , Gd + , and Tb + and also the formal closed-shell species Lu + exhibit additional C-H and C-C bond activation pathways in the reaction with fluorobenzene, namely dehydrohalogenation as well as loss of a neutral acetylene molecule. In the case of Tm + and Yb + the formation of neutral LnF 3 is observed in a multistep process via C-C coupling and charge transfer. 17 refs., 2 figs., 2 tabs

Competition between weak OH···π and CH··O hydrogen bonds: THz spectroscopy of the C2H2—H2O and C2H4—H2O complexes

DEFF Research Database (Denmark)

Andersen, Jonas; Heimdal, Jimmy; Nelander, B.

2017-01-01

an intermolecular CH⋯O hydrogen-bonded configuration of C2v symmetry with the H2O subunit acting as the hydrogen bond acceptor. The observation and assignment of two large-amplitude donor OH librational modes of the C2H4—H2O complex at 255.0 and 187.5 cm−1, respectively, confirms an intermolecular OH⋯π hydrogen...

Effective oxidation of benzylic and alkane C-H bonds catalyzed by sodium o-iodobenzenesulfonate with Oxone as a terminal oxidant under phase-transfer conditions.

Science.gov (United States)

Cui, Li-Qian; Liu, Kai; Zhang, Chi

2011-04-07

Catalytic oxidation of benzylic C-H bonds could be efficiently realized using IBS as a catalyst which was generated in situ from the oxidation of sodium 2-iodobenzenesulfonate (1b) by Oxone in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydrogen sulfate, in anhydrous acetonitrile at 60 °C. Various alkylbenzenes, including toluenes and ethylbenzenes, several oxygen-containing functionalities substituted alkylbenzenes, and a cyclic benzyl ether could be efficiently oxidized. And, the same reagent system of cat. 1b/Oxone/cat. n-Bu(4)NHSO(4) could be applied to the effective oxidation of alkanes as well.

Bite angle effects of diphosphines in C-C and C-X bond forming cross coupling reactions

NARCIS (Netherlands)

Birkholz, M.N.; Freixa, Z.; van Leeuwen, P.W.N.M.

2009-01-01

Catalytic reactions of C-C and C-X bond formation are discussed in this critical review with particular emphasis on cross coupling reactions catalyzed by palladium and wide bite angle bidentate diphosphine ligands. Especially those studies have been collected that allow comparison of the ligand bite

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

2013-11-27

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.

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; Azzi, Joachim; Abou-Hamad, Edy; Anjum, Dalaver H.; Pasha, Fahran A.; Huang, Kuo-Wei; Emsley, Lyndon; Basset, Jean-Marie

2013-01-01

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.

Synthesis and tritium labeling of the highly potent mast cell-degranulating substance P analog H-Arg-Pro-Lys-Pro-NH-C sub 12 H sub 25

Energy Technology Data Exchange (ETDEWEB)

Bienert, M.; Oehlke, J.; Niedrich, H. (Academy of Sciences of GDR, Berlin (Germany, F.R.). Inst. of Drug Research); Mittag, E. (Zentralinstitut fuer Kernforschung, Rossendorf (Germany, F.R.))

1990-12-01

Tritium labeling of the mast cell degranulating substance P analog H-Arg-Pro-Lys(3,4-{sup 3}H-Pro)-NH-C{sub 12}H{sub 25} by catalytic saturation of the dehydroproline (Dhp{sup 1}) double bond is described. Catalytic tritiation in water afforded the radioactive analog with a specific activity of 1.07 TBq/mmol. Tenfold enhancement of the catalyst-to-substrate ratio resulted in a reduced specific activity of 0.74 TBq/mmol. (author).

Hydrogenation of graphene nanoflakes and C-H bond dissociation of hydrogenated graphene nanoflakes: a density functional theory study

Institute of Scientific and Technical Information of China (English)

Sheng Tao; Hui-Ting Liu; Liu-Ming Yan; Bao-Hua Yue; Ai-Jun Li

2017-01-01

The Gibbs free energy change for the hydrogenation of graphene nanoflakes Cn (n =24,28,30 and 32) and the C-H bond dissociation energy of hydrogenated graphene nanoflakes CnHm (n =24,28,30 and 32;and m =1,2 and 3) are evaluated using density functional theory calculations.It is concluded that the graphene nanoflakes and hydrogenated graphene nanoflakes accept the ortharyne structure with peripheral carbon atoms bonded via the most triple bonds and leaving the least unpaired dangling electrons.Five-membered rings are formed at the deep bay sites attributing to the stabilization effect from the pairing of dangling electrons.The hydrogenation reactions which eliminate one unpaired dangling electron and thus decrease the overall multiplicity of the graphene nanoflakes or hydrogenated graphene nanoflakes are spontaneous with negative or near zero Gibbs free energy change.And the resulting C-H bonds are stable with bond dissociation energy in the same range as those of aromatic compounds.The other C-H bonds are not as stable attributing to the excessive unpaired dangling electrons being filled into the C-H anti-bond orbital.

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.

2008-01-30

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.

Enantioselective carbenoid insertion into C(sp3–H bonds

Directory of Open Access Journals (Sweden)

J. V. Santiago

2016-05-01

Full Text Available The enantioselective carbenoid insertion into C(sp3–H bonds is an important tool for the synthesis of complex molecules due to the high control of enantioselectivity in the formation of stereogenic centers. This paper presents a brief review of the early issues, related mechanistic studies and recent applications on this chemistry area.

Nature of active centers of catalytic system of VOCl/sub 3/ - Al(C/sub 2/H/sub 5/)/sub 2/Cl

Energy Technology Data Exchange (ETDEWEB)

Dubnikova, I L; Meshkova, I N [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1977-05-01

To investigate the nature of the active sites of the catalyst VOCl/sub 3/-Al(C/sub 2/H/sub 5/)/sub 2/Cl during olefine polymerization, the following factors have been studied: composition and catalytic activity of homogeneous and heterogeneous components of the system, valent state of vanadium entering into the composition of the catalytic sites, effect of an organoaluminium component on the catalytic activity of the system, and the properties of the polymeric products being formed. It has been shown that the catalytic sites of the system VOCl/sub 3/-Al(C/sub 4/H/sub 5/)/sub 2/Cl are located, predominantly, in the heterogeneus phase of the catalyst. A conclusion has been made that heterogeneous catalytic sites are bimetal complexes of alkyl derivatives of vanadium trichloride and aluminuim alkylchlorides and that polycentral mechanism of catalysis of olefine polymerization in the presence of VOCl/sub 3/-Al(C/sub 2/H/sub 5/)/sub 2/Cl is caused by two types of active vanadium-aluminium complexes differing in the nature of an organoaluminium component.

Oxidative C-H/C-H Cross-Coupling Reactions between N-Acylanilines and Benzamides Enabled by a Cp*-Free RhCl3/TFA Catalytic System.

Science.gov (United States)

You, Jingsong; Shi, Yang; Zhang, Luoqiang; Lan, Jingbo; Zhang, Min; Zhou, Fulin; Wei, Wenlong

2018-06-03

Using the dual chelation-assisted strategy, a completely regiocontrolled oxidative C-H/C-H cross-coupling reaction between an N-acylaniline and a benzamide has been accomplished for the first time, which enables a step-economical and highly efficient pathway to 2-amino-2'-carboxybiaryl scaffolds from readily available substrates. A Cp*-free RhCl3/TFA catalytic system has been developed to replace the generally used [Cp*RhCl2]2/AgSbF6 (Cp* = pentamethyl cyclopentadienyl) in oxidative C-H/C-H cross-coupling reactions between two (hetero)arenes. The RhCl3/TFA system avoids the use of expensive Cp* ligand and AgSbF6. As an illustrative example, the protocol developed herein greatly streamlines access to naturally occurring benzo[c]phenanthridine alkaloid oxynitidine in an excellent overall yield. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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

2014-01-08

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

Borylnitrenes: electrophilic reactive intermediates with high reactivity towards C-H bonds.

Science.gov (United States)

Bettinger, Holger F; Filthaus, Matthias

2010-12-21

Borylnitrenes (catBN 3a and pinBN 3b; cat = catecholato, pin = pinacolato) are reactive intermediates that show high tendency towards insertion into the C-H bonds of unactivated hydrocarbons. The present article summarizes the matrix isolation investigations that were aimed at identifying, characterizing and investigating the chemical behaviour of 3a by spectroscopic means, and of the experiments in solution and in the gas phase that were performed with 3b. Comparison with the reactivity reported for difluorovinylidene 1a in solid argon indicates that 3a shows by and large similar reactivity, but only after photochemical excitation. The derivative 3b inserts into the C-H bonds of hydrocarbon solvents in high yields and thus allows the formation of primary amines, secondary amines, or amides from "unreactive" hydrocarbons. It can also be used for generation of methylamine or methylamide from methane in the gas phase at room temperature. Remaining challenges in the chemistry of borylnitrenes are briefly summarized.

Selectivity control in pd-catalyzed c-h functionalization reactions

OpenAIRE

Flores Gaspar, Areli

2013-01-01

Benzocyclobutenones are an intriguing four-membered ring ketone. In the present thesis, we have developed a new protocol for selectively preparing benzocyclobutenones through intramolecular acylation of aryl bromides via palladium catalyzed C-H bond functionalization reactions based on rac-BINAP ligand. We also found that a subtle modification on the ligand backbone lead to a new catalytic manifold for preparing configurationally-pure styrene derivatives, when using dcpp (bis-dicyclohexylphos...

Mechanistic Studies of Cobalt-Catalyzed C(sp2)-H Borylation of Five-Membered Heteroarenes with Pinacolborane.

Science.gov (United States)

Obligacion, Jennifer V; Chirik, Paul J

2017-07-07

Studies into the mechanism of cobalt-catalyzed C(sp 2 )-H borylation of five-membered heteroarenes with pinacolborane (HBPin) as the boron source established the catalyst resting state as the trans -cobalt(III) dihydride boryl, ( iPr PNP)Co(H) 2 (BPin) ( iPr PNP = 2,6-( i Pr 2 PCH 2 ) 2 (C 5 H 3 N)), at both low and high substrate conversions. The overall first-order rate law and observation of a normal deuterium kinetic isotope effect on the borylation of benzofuran versus benzofuran-2- d 1 support H 2 reductive elimination from the cobalt(III) dihydride boryl as the turnover-limiting step. These findings stand in contrast to that established previously for the borylation of 2,6-lutidine with the same cobalt precatalyst, where borylation of the 4-position of the pincer occurred faster than the substrate turnover and arene C-H activation by a cobalt(I) boryl is turnover-limiting. Evaluation of the catalytic activity of different cobalt precursors in the C-H borylation of benzofuran with HBPin established that the ligand design principles for C- H borylation depend on the identities of both the arene and the boron reagent used: electron-donating groups improve catalytic activity of the borylation of pyridines and arenes with B 2 Pin 2 , whereas electron-withdrawing groups improve catalytic activity of the borylation of five-membered heteroarenes with HBPin. Catalyst deactivation by P-C bond cleavage from a cobalt(I) hydride was observed in the C-H borylation of arene substrates with C-H bonds that are less acidic than those of five-membered heteroarenes using HBPin and explains the requirement of B 2 Pin 2 to achieve synthetically useful yields with these arene substrates.

Eosin Y as a Direct Hydrogen Atom Transfer Photocatalyst for the Functionalization of C-H Bonds.

Science.gov (United States)

Fan, Xuan-Zi; Rong, Jia-Wei; Wu, Hao-Lin; Zhou, Quan; Deng, Hong-Ping; Tan, Jin Da; Xue, Cheng-Wen; Wu, Li-Zhu; Tao, Hai-Rong; Wu, Jie

2018-05-02

Eosin Y, a well-known economical alternative to metal catalysts in visible-light-driven single-electron transfer-based organic transformations, can behave as an effective direct hydrogen atom transfer catalyst for C-H activation. Using the alkylation of C-H bonds with electron-deficient alkenes as a model study revealed an extremely broad substrate scope, enabling easy access to a variety of important synthons. This eosin Y-based photocatalytic hydrogen atom transfer strategy is promising for diverse functionalization of a wide range of native C-H bonds in a green and sustainable manner. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct α-C-H bond functionalization of unprotected cyclic amines

Science.gov (United States)

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

2018-02-01

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.

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.

Science.gov (United States)

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

2016-05-18

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)).

Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

Science.gov (United States)

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

2017-09-19

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

Cobalt-Catalyzed, Aminoquinoline-Directed sp2 C-H Bond Alkenylation by Alkynes**

Science.gov (United States)

Grigorjeva, Liene; Daugulis, Olafs

2014-01-01

We have developed a method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed sp2 C-H bond alkenylation by alkynes. Method shows excellent functional group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs Co(OAc)2*4H2O catalyst, Mn(OAc)2 cocatalyst, and oxygen from air as a terminal oxidant. PMID:25060365

Reversible Heterolytic Cleavage of the H-H Bond by Molybdenum Complexes: Controlling the Dynamics of Exchange Between Proton and Hydride

Energy Technology Data Exchange (ETDEWEB)

Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris

2017-05-18

Controlling the heterolytic cleavage of the H-H bond of dihydrogen is critically important in catalytic hydrogenations and in the catalytic oxidation of H2. We show how the rate of reversible heterolytic cleavage of H2 can be controlled over nearly four orders of magnitude at 25 °C, from 2.1 × 103 s-1 to ≥107 s-1. Bifunctional Mo complexes, [CpMo(CO)(κ3-P2N2)]+ (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane with alkyl/aryl groups on N and P), have been developed for heterolytic cleavage of H2 into a proton and a hydride, akin to Frustrated Lewis Pairs. The H-H bond cleavage is enabled by the basic amine in the second coordination sphere. The products of heterolytic cleavage of H2, Mo hydride complexes bearing protonated amines, [CpMo(H)(CO)(P2N2H)]+, were characterized by spectroscopic studies and by X-ray crystallography. Variable temperature 1H, 15N and 2-D 1H-1H ROESY NMR spectra indicated rapid exchange of the proton and hydride. The exchange rates are in the order [CpMo(H)(CO)(PPh2NPh2H)]+ > [CpMo(H)(CO)(PtBu2NPh2H)]+ > [CpMo(H)(CO)(PPh2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NtBu2H)]+. The pKa values determined in acetonitrile range from 9.3 to 17.7, and show a linear correlation with the logarithm of the exchange rates. Thus the exchange dynamics are controlled through the relative acidity of the [CpMo(H)(CO)(P2N2H)]+ and [CpMo(H2)(CO)(P2N2)]+ isomers, providing a design principle for controlling heterolytic cleavage of H2.

Detection and function of an intramolecular disulfide bond in the pH-responsive CadC of Escherichia coli

Directory of Open Access Journals (Sweden)

Dönhöfer Alexandra

2011-04-01

Full Text Available Abstract Background In an acidic and lysine-rich environment Escherichia coli induces expression of the cadBA operon which encodes CadA, the lysine decarboxylase, and CadB, the lysine/cadaverine antiporter. cadBA expression is dependent on CadC, a membrane-integrated transcriptional activator which belongs to the ToxR-like protein family. Activation of CadC requires two stimuli, lysine and low pH. Whereas lysine is detected by an interplay between CadC and the lysine-specific transporter LysP, pH alterations are sensed by CadC directly. Crystal structural analyses revealed a close proximity between two periplasmic cysteines, Cys208 and Cys272. Results Substitution of Cys208 and/or Cys272 by alanine resulted in CadC derivatives that were active in response to only one stimulus, either lysine or pH 5.8. Differential in vivo thiol trapping revealed a disulfide bond between these two residues at pH 7.6, but not at pH 5.8. When Cys208 and Cys272 were replaced by aspartate and lysine, respectively, virtually wild-type behavior was restored indicating that the disulfide bond could be mimicked by a salt bridge. Conclusion A disulfide bond was found in the periplasmic domain of CadC that supports an inactive state of CadC at pH 7.6. At pH 5.8 disulfide bond formation is prevented which transforms CadC into a semi-active state. These results provide new insights into the function of a pH sensor.

Ligand-enabled ortho-C-H olefination of phenylacetic amides with unactivated alkenes.

Science.gov (United States)

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

2018-02-07

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.

Cobalt-catalyzed, aminoquinoline-directed C(sp²)-H bond alkenylation by alkynes.

Science.gov (United States)

Grigorjeva, Liene; Daugulis, Olafs

2014-09-15

A method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed C(sp(2))-H bond alkenylation by alkynes was developed. The method shows excellent functional-group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs a Co(OAc)2⋅4 H2O catalyst, Mn(OAc)2 co-catalyst, and oxygen (from air) as a terminal oxidant. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of silyl iron hydride via Si-H activation and its dual catalytic application in the hydrosilylation of carbonyl compounds and dehydration of benzamides.

Science.gov (United States)

Ren, Shishuai; Xie, Shangqing; Zheng, Tingting; Wang, Yangyang; Xu, Shilu; Xue, Benjing; Li, Xiaoyan; Sun, Hongjian; Fuhr, Olaf; Fenske, Dieter

2018-03-28

The hydrido silyl iron complex (o-Ph 2 PC 6 H 4 SiMe 2 )Fe(PMe 3 ) 3 H (2) was obtained via the activation of the Si-H bond of the bidentate silyl ligand o-Ph 2 P(C 6 H 4 )SiMe 2 H (1) by Fe(PMe 3 ) 4 . 2 showed good to excellent catalytic activity in both the reduction of aldehydes/ketones and the dehydration of benzamide. In addition, with complex 2 as a catalyst, α,β-unsaturated carbonyls could be selectively reduced to the corresponding α,β-unsaturated alcohols. The mechanisms of the formation of 2 and the catalytic dehydration process are proposed and partly experimentally verified.

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

KAUST Repository

Poater, Albert

2016-09-11

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.

CO-Bridged H-Cluster Intermediates in the Catalytic Mechanism of [FeFe]-Hydrogenase CaI.

Science.gov (United States)

Ratzloff, Michael W; Artz, Jacob H; Mulder, David W; Collins, Reuben T; Furtak, Thomas E; King, Paul W

2018-06-20

The [FeFe]-hydrogenases ([FeFe] H 2 ases) catalyze reversible H 2 activation at the H-cluster, which is composed of a [4Fe-4S] H subsite linked by a cysteine thiolate to a bridged, organometallic [2Fe-2S] ([2Fe] H ) subsite. Profoundly different geometric models of the H-cluster redox states that orchestrate the electron/proton transfer steps of H 2 bond activation have been proposed. We have examined this question in the [FeFe] H 2 ase I from Clostridium acetobutylicum (CaI) by Fourier-transform infrared (FTIR) spectroscopy with temperature annealing and H/D isotope exchange to identify the relevant redox states and define catalytic transitions. One-electron reduction of H ox led to formation of H red H + ([4Fe-4S] H 2+ -Fe I -Fe I ) and H red ' ([4Fe-4S] H 1+ -Fe II -Fe I ), with both states characterized by low frequency μ-CO IR modes consistent with a fully bridged [2Fe] H . Similar μ-CO IR modes were also identified for H red H + of the [FeFe] H 2 ase from Chlamydomonas reinhardtii (CrHydA1). The CaI proton-transfer variant C298S showed enrichment of an H/D isotope-sensitive μ-CO mode, a component of the hydride bound H-cluster IR signal, H hyd . Equilibrating CaI with increasing amounts of NaDT, and probed at cryogenic temperatures, showed H red H + was converted to H hyd . Over an increasing temperature range from 10 to 260 K catalytic turnover led to loss of H hyd and appearance of H ox , consistent with enzymatic turnover and H 2 formation. The results show for CaI that the μ-CO of [2Fe] H remains bridging for all of the "H red " states and that H red H + is on pathway to H hyd and H 2 evolution in the catalytic mechanism. These results provide a blueprint for designing small molecule catalytic analogs.

New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

KAUST Repository

Samantaray, Manoja; Dey, Raju; Kavitake, Santosh Giridhar; Basset, Jean-Marie

2015-01-01

In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C

Tritium labeled Gentamicin C : II.- Bioradioactive products of Gentamicin by Catalytic H2O-3H exchange reaction

International Nuclear Information System (INIS)

Suarez, C.; Diaz, A.; Paz, D.; Jimeno, M.L.

1992-01-01

The main bioradioactive degradation products from catalytic hydrogen exchange of gentamicin C, (C1 + C2 + C1a) in basic form, are generated by N-dimethylations in 3 - N and 6'-N positions. Their structures were confirmed by HNMR and 13 CNMR. These derivatives were fractionated by chromatography on silica gel. Antibacterial activities were similar to those of the parent antibiotics. Tritium exchange, under vacuum or nitrogen, is highly increased (4:1) when gentamicina are in basic form. In contrast with gentamicin sulfate, hydrolytic subproducts as garamine, gentamicine, garosamine and purpurosamines are practically absent. To properly optimize the exchange process, the composition of the gentamicin C complex must be taken into account. The exchange decreases in the order C2 > C1 > C1a. Because of 6' -N-dimenthyl gentamicin C1 is C2, the radiochemical yield of C2 appears enhanced in the H 2 O- 3 H exchange of a mixture of them. Radioactivity distribution among the components and subunits of these three gentamicins were studied by stron and mild hydrolysis, and by methanolysis. (author)

Study of the adsorption, electronic structure and bonding of C2H4 on the FeNi(1 1 1) surface

International Nuclear Information System (INIS)

Simonetti, S.; Brizuela, G.; Juan, A.

2010-01-01

The adsorption of C 2 H 4 on the FeNi(1 1 1) alloy surface has been studied by ASED-MO tight binding calculations. The C 2 H 4 molecule presents its most stable geometry with the C=C bond axis parallel to the surface along the [1, -1, 0] direction, bonded on top Fe atom and bonded along a Fe-Fe bridge site. As a consequence, the strength of the local Fe-Fe bond decreases between 37 and 62% of its original bulk value. This bond weakening is mainly due to the new C-Fe interactions however no Fe 3 C carbide formation is evidenced on surface. The Fe-Ni and Ni-Ni superficial bonds are only slightly modified.

Forging C-C Bonds Through Decarbonylation of Aryl Ketones.

Science.gov (United States)

Somerville, Rosie J; Martin, Ruben

2017-06-06

The ability of nickel to cleave strong σ-bonds is again in the spotlight after a recent report that demonstrates the feasibility of using nickel complexes to promote decarbonylation of diaryl ketones. This transformation involves the cleavage of two strong C-C(O) bonds and avoids the use of noble metals, hence reinforcing the potential of decarbonylation as a technique for forging C-C bonds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cu-catalyzed C(sp³)-H bond activation reaction for direct preparation of cycloallyl esters from cycloalkanes and aromatic aldehydes.

Science.gov (United States)

Zhao, Jincan; Fang, Hong; Han, Jianlin; Pan, Yi

2014-05-02

Cu-catalyzed dehydrogenation-olefination and esterification of C(sp(3))-H bonds of cycloalkanes with TBHP as an oxidant has been developed. The reaction involves four C-H bond activations and gives cycloallyl ester products directly from cycloalkanes and aromatic aldehydes.

Facile Synthesis and Superior Catalytic Activity of Nano-TiN@N-C for Hydrogen Storage in NaAlH4.

Science.gov (United States)

Zhang, Xin; Ren, Zhuanghe; Lu, Yunhao; Yao, Jianhua; Gao, Mingxia; Liu, Yongfeng; Pan, Hongge

2018-05-09

Herein, we synthesize successfully ultrafine TiN nanoparticles (hydrogen storage in NaAlH 4 . Adding 7 wt % nano-TiN@N-C induces more than 100 °C reduction in the onset dehydrogenation temperature of NaAlH 4 . Approximately 4.9 wt % H 2 is rapidly released from the 7 wt % nano-TiN@N-C-containing NaAlH 4 at 140 °C within 60 min, and the dehydrogenation product is completely hydrogenated at 100 °C within 15 min under 100 bar of hydrogen, exhibiting significantly improved desorption/absorption kinetics. No capacity loss is observed for the nano-TiN@N-C-containing sample within 25 de-/hydrogenation cycles because nano-TiN functions as an active catalyst instead of a precursor. A severe structural distortion with extended bond lengths and reduced bond strengths for Al-H bonding when the [AlH 4 ] - group adsorbs on the TiN cluster is demonstrated for the first time by density functional theory calculations, which well-explains the reduced de-/hydrogenation temperatures of the nano-TiN@N-C-containing NaAlH 4 . These findings provide new insights into designing and synthesizing high-performance catalysts for hydrogen storage in complex hydrides.

Cat-CVD-prepared oxygen-rich μc-Si:H for wide-bandgap material

International Nuclear Information System (INIS)

Matsumoto, Yasuhiro; Ortega, Mauricio; Peza, Juan-Manuel; Reyes, Mario-Alfredo; Escobosa, Arturo

2005-01-01

Microcrystalline phase-involved oxygen-rich a-Si:H (hydrogenated amorphous silicon) films have been obtained using catalytic chemical vapor deposition (Cat-CVD) process. Pure SiH 4 (silane), H 2 (hydrogen), and O 2 (oxygen) gases were introduced in the chamber by maintaining a pressure of 0.1 Torr. A tungsten catalyzer was fixed at temperatures of 1750 and 1950 deg. C for film deposition on glass and crystalline silicon substrates at 200 deg. C. As revealed from X-ray diffraction spectra, the microcrystalline phase appears for oxygen-rich a-Si:H samples deposited at a catalyzer temperature of 1950 deg. C. However, this microcrystalline phase tends to disappear for further oxygen incorporation. The oxygen content in the deposited films was corroborated by FTIR analysis revealing Si-O-Si bonds and typical Si-H bonding structures. The optical bandgap of the sample increases from 2.0 to 2.7 eV with oxygen gas flow and oxygen incorporation to the deposited films. In the present thin film deposition conditions, no strong tungsten filament degradation was observed after a number of sample preparations

Aerobic Asymmetric Dehydrogenative Cross-Coupling between Two C(sp3)-H Groups Catalyzed by a Chiral-at-Metal Rhodium Complex.

Science.gov (United States)

Tan, Yuqi; Yuan, Wei; Gong, Lei; Meggers, Eric

2015-10-26

A sustainable C-C bond formation is merged with the catalytic asymmetric generation of one or two stereocenters. The introduced catalytic asymmetric cross-coupling of two C(sp3)-H groups with molecular oxygen as the oxidant profits from the oxidative robustness of a chiral-at-metal rhodium(III) catalyst and exploits an autoxidation mechanism or visible-light photosensitized oxidation. In the latter case, the catalyst serves a dual function, namely as a chiral Lewis acid for catalyzing enantioselective enolate chemistry and at the same time as a visible-light-driven photoredox catalyst. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Merging Visible Light Photoredox Catalysis with Metal Catalyzed C–H Activations: On the Role of Oxygen and Superoxide Ions as Oxidants

KAUST Repository

Fabry, David C.; Rueping, Magnus

2016-01-01

ConspectusThe development of efficient catalytic systems for direct aromatic C-H bond functionalization is a long-desired goal of chemists, because these protocols provide environmental friendly and waste-reducing alternatives to classical methodologies for C-C and C-heteroatom bond formation. A key challenge for these transformations is the reoxidation of the in situ generated metal hydride or low-valent metal complexes of the primary catalytic bond forming cycle. To complete the catalytic cycle and to regenerate the C-H activation catalyst, (super)stoichiometric amounts of Cu(II) or Ag(I) salts have often been applied. Recently,

Merging Visible Light Photoredox Catalysis with Metal Catalyzed C–H Activations: On the Role of Oxygen and Superoxide Ions as Oxidants

KAUST Repository

Fabry, David C.

2016-08-24

ConspectusThe development of efficient catalytic systems for direct aromatic C-H bond functionalization is a long-desired goal of chemists, because these protocols provide environmental friendly and waste-reducing alternatives to classical methodologies for C-C and C-heteroatom bond formation. A key challenge for these transformations is the reoxidation of the in situ generated metal hydride or low-valent metal complexes of the primary catalytic bond forming cycle. To complete the catalytic cycle and to regenerate the C-H activation catalyst, (super)stoichiometric amounts of Cu(II) or Ag(I) salts have often been applied. Recently,

Structure and function of C-terminal catalytic region of pasteurella multocida toxin

International Nuclear Information System (INIS)

Kitadokoro, Kengo; Kamitami, Shigeki; Horiguchi, Yasuhiko

2008-01-01

Pasteurella multocida toxin (PMT) is one of virulence factors responsible for the pathogenesis in some Pasteurellosis. We determined the crystal structure of the C-terminal region of PMT (C-PMT), which carries an intracellularly active moiety. The overall structure of C-PMT displays three different domains designated C1, C2 and C3. We found in the C3 domain the Cys-His-Asp catalytic triad that is organized only when the Cys is released from a disulfide bond. The steric alignment of the triad corresponded well to that of papain or other enzymes carrying the Cys-His-Asp triad. Our results demonstrate that PMT is an enzymatic toxin carrying the cysteine-protease like catalytic triad, which is organized only under reducing conditions. (author)

Electrochemical promotion of catalytic reactions with Pt/C (or Pt/Ru/C)//PBI catalysts

DEFF Research Database (Denmark)

Petrushina, Irina; Bjerrum, Niels; Bandur, Viktor

2007-01-01

The paper is an overview of the results of the investigation on electrochemical promotion of three catalytic reactions: methane oxidation with oxygen, NO reduction with hydrogen at 135 degrees C and Fischer-Tropsch synthesis (FTS) at 170 degrees C in the [CH4/O-2(or NO/H-2 or CO/H-2)/Ar//Pt(or Pt....../Ru)//PBI(H3PO4)/H-2, Ar] fuel cell. It has been shown that the partial methane oxidation to C2H2 and the C-2 selectivity were electrochemically promoted by the negative catalyst polarization. This was also the case in NO reduction with hydrogen for low NO and H-2 partial pressures. In both cases the catalytic...... reactions have been promoted by the electrochemically produced hydrogen. It has been found that the NO reduction with hydrogen on the Pt/PBI strongly depends on NO and hydrogen partial pressures in the working gas mixture. At higher NO and H-2 partial pressures the catalysis is promoted...

Tritium Labeled Gentamicin C: II.- Bioradiactive Degradation Products of Gentamicin by Catalytic H2O-3H Exchange Reaction

International Nuclear Information System (INIS)

Suarez, C.; Diaz, A.; Paz, D.; Jimeno, M. L.

1992-01-01

The main bio radioactive degradation products from catalytic hydrogen exchange of gentamicin C, (C1 + C2 + Cla) in basic form, are generated by N-demethylation in 3 - N and 6-N positions. Their structures were confirmed by 1HNMR and 13CNMR. These derivatives were fractionated by chromatography on silica gel. Antibacterial activities were similar to those of the parent antibiotics. Tritium exchange, under vacuum or nitrogen, is highly increased (4:1) when gentamicin are in basic form. In contrast with gentamicin sulfate, hydrolytic sub products as gramine, genta mines, garosamine and purpurosamines are practically absent. To properly optimize the exchange process, the composition of the gentamicin C complex must be taken into account. The exchange decreases in the order C2 > C1> Cla. Because of 6'-N-demethyl gentamicin C1 is C2, the radiochemical yield of C2 appears enhanced in the H2O-3H exchange of a mixture of them. Radioactivity distribution among the components and subunits of these three gentamicin were studied by strong and mild hydrolysis, and by methanolysis. (Author) 18 refs

Rhodium(III)-Catalyzed Activation of C(sp3)-H Bonds and Subsequent Intermolecular Amidation at Room Temperature.

Science.gov (United States)

Huang, Xiaolei; Wang, Yan; Lan, Jingbo; You, Jingsong

2015-08-03

Disclosed herein is a Rh(III)-catalyzed chelation-assisted activation of unreactive C(sp3)-H bonds, thus enabling an intermolecular amidation to provide a practical and step-economic route to 2-(pyridin-2-yl)ethanamine derivatives. Substrates with other N-donor groups are also compatible with the amidation. This protocol proceeds at room temperature, has a relatively broad functional-group tolerance and high selectivity, and demonstrates the potential of rhodium(III) in the promotive functionalization of unreactive C(sp3)-H bonds. A rhodacycle having a SbF6(-) counterion was identified as a plausible intermediate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of 14C- and 3H-labeled fluoxetine, a selective serotonin uptake inhibitor

International Nuclear Information System (INIS)

Robertson, D.W.; Krushinski, J.H.; Wong, D.T.; Kau, D.

1987-01-01

Fluoxetine (N-methyl-γ-(4-(trifluoromethyl)phenoxy) benzenepropanamine) is a potent, highly selective serotonin uptake inhibitor that is useful in treating a variety of major psychiatric derangements. We have synthesized this compound in 14 C- and 3 H-labeled forms. The tritium label was introduced in the final step by catalytic dehalogenation of the brominated fluoxetine precursor. Reaction conditions could be controlled such that catalytic hydrogenolysis of the labile C-O benzylic bond was minimized. Following HPLC purification, [ 3 H]-fluoxetine was obtained in a state of high radiochemical purity (98%) and specific activity (20.4 Ci/mmol). The 14 C-label was introduced in the final step via a nucleophilic aromatic substitution reaction between the sodium salt of α-(2-(methylamino)ethyl)benzenemethanol and uniformly ring-labeled p-chlorobenzotrifluoride. Following purification by flash chromatography, [ 14 C]-fluoxetine was obtained in 98.3% radiochemical purity with a specific activity of 5.52 mCi/mmol. (author)

Multifaceted catalytic hydrogenation of amides via diverse activation of a sterically confined bipyridine-ruthenium framework.

Science.gov (United States)

Miura, Takashi; Naruto, Masayuki; Toda, Katsuaki; Shimomura, Taiki; Saito, Susumu

2017-05-16

Amides are ubiquitous and abundant in nature and our society, but are very stable and reluctant to salt-free, catalytic chemical transformations. Through the activation of a "sterically confined bipyridine-ruthenium (Ru) framework (molecularly well-designed site to confine adsorbed H 2 in)" of a precatalyst, catalytic hydrogenation of formamides through polyamide is achieved under a wide range of reaction conditions. Both C=O bond and C-N bond cleavage of a lactam became also possible using a single precatalyst. That is, catalyst diversity is induced by activation and stepwise multiple hydrogenation of a single precatalyst when the conditions are varied. The versatile catalysts have different structures and different resting states for multifaceted amide hydrogenation, but the common structure produced upon reaction with H 2 , which catalyzes hydrogenation, seems to be "H-Ru-N-H."

13C NMR spectra and bonding situation of the B-C bond in alkynylboranes

International Nuclear Information System (INIS)

Yamamoto, Yoshinori; Moritani, Ichiro

1975-01-01

13 C NMR spectra of boron substituted alkynes reveal that the β-carbon is deshielded by ca. 21 ppm by a B(O-n-C 4 H 9 ) 2 group. This clearly indicates the presence of a B-C π-bonding in alkynylboranes. (auth.)

UV-light promoted C-H bond activation of benzene and fluorobenzenes by an iridium(i) pincer complex.

Science.gov (United States)

Hauser, Simone A; Emerson-King, Jack; Habershon, Scott; Chaplin, Adrian B

2017-03-28

Iridium(i) carbonyl complex [Ir(2,6-(P t Bu 2 CH 2 ) 2 C 6 H 3 )(CO)] undergoes reversible C-H bond activation of benzene and a series of fluorobenzenes on UV irradiation. Exclusive ortho-selectivity is observed in reactions of fluorobenzene and 1,2-difluorobenzene.

UV photolysis of 4-iodo-, 4-bromo-, and 4-chlorophenol: competition between C-Y (Y = halogen) and O-H bond fission.

Science.gov (United States)

Sage, Alan G; Oliver, Thomas A A; King, Graeme A; Murdock, Daniel; Harvey, Jeremy N; Ashfold, Michael N R

2013-04-28

The wavelength dependences of C-Y and O-H bond fission following ultraviolet photoexcitation of 4-halophenols (4-YPhOH) have been investigated using a combination of velocity map imaging, H Rydberg atom photofragment translational spectroscopy, and high level spin-orbit resolved electronic structure calculations, revealing a systematic evolution in fragmentation behaviour across the series Y = I, Br, Cl (and F). All undergo O-H bond fission following excitation at wavelengths λ ≲ 240 nm, on repulsive ((n∕π)σ∗) potential energy surfaces (PESs), yielding fast H atoms with mean kinetic energies ∼11,000 cm(-1). For Y = I and Br, this process occurs in competition with prompt C-I and C-Br bond cleavage on another (n∕π)σ∗ PES, but no Cl∕Cl∗ products unambiguously attributable to one photon induced C-Cl bond fission are observed from 4-ClPhOH. Differences in fragmentation behaviour at longer excitation wavelengths are more marked. Prompt C-I bond fission is observed following excitation of 4-IPhOH at all λ ≤ 330 nm; the wavelength dependent trends in I∕I∗ product branching ratio, kinetic energy release, and recoil anisotropy suggest that (with regard to C-I bond fission) 4-IPhOH behaves like a mildly perturbed iodobenzene. Br atoms are observed when exciting 4-BrPhOH at long wavelengths also, but their velocity distributions suggest that dissociation occurs after internal conversion to the ground state. O-H bond fission, by tunnelling (as in phenol), is observed only in the cases of 4-FPhOH and, more weakly, 4-ClPhOH. These observed differences in behaviour can be understood given due recognition of (i) the differences in the vertical excitation energies of the C-Y centred (n∕π)σ∗ potentials across the series Y = I bond strength, cf. that of the rival O-H bond, and (ii) the much increased spin-orbit coupling in, particularly, 4-IPhOH. The present results provide (another) reminder of the risks inherent in extrapolating photochemical

Competition between weak OH···π and CH··O hydrogen bonds: THz spectroscopy of the C₂H₂—H₂O and C₂H₄—H₂O complexes

DEFF Research Database (Denmark)

Andersen, Jonas; Heimdal, Jimmy; Nelander, B.

2017-01-01

-bonded configuration with the H2O subunit acting as the hydrogen bond donor to the π-cloud of C2H4. A (semi)-empirical value for the change of vibrational zero-point energy of 4.0–4.1 kJ mol−1 is proposed and the combination with quantum chemical calculations at the CCSD(T)-F12b/aug-cc-pVQZ level provides a reliable....... The present findings demonstrate that the relative stability of the weak hydrogen bond motifs is not entirely rooted in differences of electronic energy but also to a large extent by differences in the vibrational zero-point energy contributions arising from the class of large-amplitude intermolecular modes....... estimate of 7.1 ± 0.3 kJ mol−1 for the dissociation energy D0 of the C2H4—H2O complex. In addition, tentative assignments for the two strongly infrared active OH librational modes of the ternary C2H4—HOH—C2H4 complex having H2O as a doubly OH⋯π hydrogen bond donor are proposed at 213.6 and 222.3 cm−1...

Nonperfect synchronization of bond-forming and bond-rupturing processes in the reaction H + H2 → H2 + H

International Nuclear Information System (INIS)

Chandra, A.K.; Rao, V.S.

1996-01-01

The simplest prototypical hydrogen transfer reaction, i.e., H + H 2 → H 2 + H, is studied by the quantum-mechanical ab initio methods. Results reveal that during this reaction free valence which almost equals the square of the spin density develops on the migrating hydrogen atom. Bond orders are calculated using Mayer's formalism. Both the variations of bond orders and bond lengths along the reaction path are examined. This analysis reveals that the bond formation and bond cleavage processes in this reaction are not perfectly synchronous. The bond clevage process is slightly more advanced on the reaction path. 38 refs., 6 figs., 2 tabs

Um estudo teórico de propriedades moleculares em complexos de hidrogênio trimoleculares C2H4···2HF, C2H2···2HF e C3h6···2HF A theoretical study of molecular properties of C2H4···2HF, C2H2···2HF AND C3H6···2HF trimolecular hydrogen-bonded complexes

Directory of Open Access Journals (Sweden)

Boaz G. Oliveira

2008-01-01

Full Text Available We present a theoretical study of molecular properties in C2H4···2HF, C2H2···2HF and C3H6···2HF trimolecular hydrogen-bonded complexes. From B3LYP/6-311++G(d,p calculations, the most important structural deformations are related to the C=C (C2H4, C≡C (C2H2, C-C (C3H6 and HF bond lengths. According to the Bader's atoms in molecules and CHELPG calculations, it was identified a tertiary interaction between the fluorine atom of the second hydrofluoric acid molecule and hydrogen atoms of the ethylene and acetylene within the C2H4···2HF and C2H2···2HF complexes, respectively. Additionally, the evaluation of the infrared spectrum characterized the new vibrational modes and bathochromic effect of the HF molecules.

Measurement of 2J(H,C)- and 3J(H,C)-coupling constants by α/β selective HC(C)H-TOCSY

International Nuclear Information System (INIS)

Duchardt, Elke; Richter, Christian; Reif, Bernd; Glaser, Steffen J.; Engels, Joachim W.; Griesinger, Christian; Schwalbe, Harald

2001-01-01

A new heteronuclear NMR pulse sequence for the measurement of n J(C,H) coupling constants, the α/βselective HC(C)H-TOCSY, is described. It is shown that the S 3 E element (Meissner et al., 1997a,b) can be used to obtain spin state selective coherence transfer in molecules, in which adjacent CH moieties are labeled with 13 C. Application of the α/β selective HC(C)H-TOCSY to a 10nt RNA tetraloop 5'-CGCUUUUGCG-3', in which the four uridine residues are 13 C labeled in the sugar moiety, allowed measurement of two bond and three bond J(C,H) coupling constants, which provide additional restraints to characterize the sugar ring conformation of RNA in cases of conformational averaging

Molecularly Tuning the Radicaloid N-H···O═C Hydrogen Bond.

Science.gov (United States)

Lu, Norman; Chung, Wei-Cheng; Ley, Rebecca M; Lin, Kwan-Yu; Francisco, Joseph S; Negishi, Ei-Ichi

2016-03-03

Substituent effects on the open shell N-H···O═C hydrogen-bond has never been reported. This study examines how 12 functional groups composed of electron donating groups (EDG), halogen atoms and electron withdrawing groups (EWG) affect the N-H···O═C hydrogen-bond properties in a six-membered cyclic model system of O═C(Y)-CH═C(X)N-H. It is found that group effects on this open shell H-bonding system are significant and have predictive trends when X = H and Y is varied. When Y is an EDG, the N-H···O═C hydrogen-bond is strengthened; and when Y is an EWG, the bond is weakened; whereas the variation in electronic properties of X group do not exhibit a significant impact upon the hydrogen bond strength. The structural impact of the stronger N-H···O═C hydrogen-bond are (1) shorter H and O distance, r(H···O) and (2) a longer N-H bond length, r(NH). The stronger N-H···O═C hydrogen-bond also acts to pull the H and O in toward one another which has an effect on the bond angles. Our findings show that there is a linear relationship between hydrogen-bond angle and N-H···O═C hydrogen-bond energy in this unusual H-bonding system. In addition, there is a linear correlation of the r(H···O) and the hydrogen bond energy. A short r(H···O) distance corresponds to a large hydrogen bond energy when Y is varied. The observed trends and findings have been validated using three different methods (UB3LYP, M06-2X, and UMP2) with two different basis sets.

C-H Bond Functionalization via Hydride Transfer: Formation of α-Arylated Piperidines and 1,2,3,4-Tetrahydroisoquinolines via Stereoselective Intramolecular Amination of Benzylic C-H Bonds

OpenAIRE

Vadola, Paul A.; Carrera, Ignacio; Sames, Dalibor

2012-01-01

We here report a study of the intramolecular amination of sp3 C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl-aldehydes are subjected to N-toluenesulfonamide in the presence of BF3•OEt2 to effect imine formation and HT-cyclization, leading to 2-aryl-piperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexib...

Binding of hydrocarbons and other extremely weak ligands to transition metal complexes that coordinate hydrogen: Investigation of cis-interactions and delocalized bonding involving sigma bonds

International Nuclear Information System (INIS)

Kubas, G.J.; Eckert, J.; Luo, X.L.

1997-01-01

This is the final report of a three-year Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). At the forefront of chemistry are efforts to catalytically transform the inert C-H bonds in alkanes to more useful products using metal compounds. The goal is to observe binding and cleavage of alkane C-H bonds on metals or to use related silane Si-H bonding as models, analogous to the discovery of hydrogen (H 2 ) binding to metals. Studies of these unique sigma complexes (M hor-ellipsis H-Y; Y double-bond H, Si, C) will aid in developing new catalysts or technologies relevant to DOE interest, e.g., new methods for tritium isotope separation. Several transition metals (Mo, W, Mn, and Pt) were found to reversibly bind and cleave H 2 , silanes, and halocarbons. The first metal-SiH 4 complexes, thus serving as a model for methane reactions. A second goal is to study the dynamics and energetics of H-Y bonds on metals by neutron scattering, and evidence for interactions between bound H-Y and nearby H atoms on metal complexes has been found

A conserved hydrogen-bond network in the catalytic centre of animal glutaminyl cyclases is critical for catalysis.

Science.gov (United States)

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

2008-04-01

QCs (glutaminyl cyclases; glutaminyl-peptide cyclotransferases, EC 2.3.2.5) 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.

UV photolysis of 4-iodo-, 4-bromo-, and 4-chlorophenol: Competition between C-Y (Y = halogen) and O-H bond fission

Science.gov (United States)

Sage, Alan G.; Oliver, Thomas A. A.; King, Graeme A.; Murdock, Daniel; Harvey, Jeremy N.; Ashfold, Michael N. R.

2013-04-01

The wavelength dependences of C-Y and O-H bond fission following ultraviolet photoexcitation of 4-halophenols (4-YPhOH) have been investigated using a combination of velocity map imaging, H Rydberg atom photofragment translational spectroscopy, and high level spin-orbit resolved electronic structure calculations, revealing a systematic evolution in fragmentation behaviour across the series Y = I, Br, Cl (and F). All undergo O-H bond fission following excitation at wavelengths λ ≲ 240 nm, on repulsive ((n/π)σ*) potential energy surfaces (PESs), yielding fast H atoms with mean kinetic energies ˜11 000 cm-1. For Y = I and Br, this process occurs in competition with prompt C-I and C-Br bond cleavage on another (n/π)σ* PES, but no Cl/Cl* products unambiguously attributable to one photon induced C-Cl bond fission are observed from 4-ClPhOH. Differences in fragmentation behaviour at longer excitation wavelengths are more marked. Prompt C-I bond fission is observed following excitation of 4-IPhOH at all λ ≤ 330 nm; the wavelength dependent trends in I/I* product branching ratio, kinetic energy release, and recoil anisotropy suggest that (with regard to C-I bond fission) 4-IPhOH behaves like a mildly perturbed iodobenzene. Br atoms are observed when exciting 4-BrPhOH at long wavelengths also, but their velocity distributions suggest that dissociation occurs after internal conversion to the ground state. O-H bond fission, by tunnelling (as in phenol), is observed only in the cases of 4-FPhOH and, more weakly, 4-ClPhOH. These observed differences in behaviour can be understood given due recognition of (i) the differences in the vertical excitation energies of the C-Y centred (n/π)σ* potentials across the series Y = I increased spin-orbit coupling in, particularly, 4-IPhOH. The present results provide (another) reminder of the risks inherent in extrapolating photochemical behaviour measured for one molecule at one wavelength to other (related) molecules and to

Conformation-induced remote meta-C-H activation of amines

Science.gov (United States)

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

2014-03-01

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.

Hypovalency--a kinetic-energy density description of a 4c-2e bond.

Science.gov (United States)

Jacobsen, Heiko

2009-06-07

A bond descriptor based on the kinetic energy density, the localized-orbital locator (LOL), is used to characterize the nature of the chemical bond in electron deficient multi-center bonds. The boranes B(2)H(6), B(4)H(4), B(4)H(10), [B(6)H(6)](2-), and [B(6)H(7)](-) serve as prototypical examples of hypovalent 3c-2e and 4c-2e bonding. The kinetic energy density is derived from a set of Kohn-Sham orbitals obtained from pure density functional calculations (PBE/TZVP), and the topology of LOL is analyzed in terms of (3,-3) attractors (Gamma). The B-B-B and B-H-B 3c-2e, and the B-B-H-B 4c-2e bonding situations are defined by their own characteristic LOL profiles. The presence of one attractor in relation to the three or four atoms that are engaged in electron deficient bonding provides sufficient indication of the type of 3c-2e or 4c-2e bond present. For the 4c-2e bond in [B(6)H(7)](-) the LOL analysis is compared to results from an experimental QTAIM study.

Synthesis of /sup 14/C- and /sup 3/H-labeled fluoxetine, a selective serotonin uptake inhibitor

Energy Technology Data Exchange (ETDEWEB)

Robertson, D.W.; Krushinski, J.H.; Wong, D.T.; Kau, D.

1987-11-01

Fluoxetine (N-methyl-..gamma..-(4-(trifluoromethyl)phenoxy) benzenepropanamine) is a potent, highly selective serotonin uptake inhibitor that is useful in treating a variety of major psychiatric derangements. We have synthesized this compound in /sup 14/C- and /sup 3/H-labeled forms. The tritium label was introduced in the final step by catalytic dehalogenation of the brominated fluoxetine precursor. Reaction conditions could be controlled such that catalytic hydrogenolysis of the labile C-O benzylic bond was minimized. Following HPLC purification, (/sup 3/H)-fluoxetine was obtained in a state of high radiochemical purity (98%) and specific activity (20.4 Ci/mmol). The /sup 14/C-label was introduced in the final step via a nucleophilic aromatic substitution reaction between the sodium salt of ..cap alpha..-(2-(methylamino)ethyl)benzenemethanol and uniformly ring-labeled p-chlorobenzotrifluoride. Following purification by flash chromatography, (/sup 14/C)-fluoxetine was obtained in 98.3% radiochemical purity with a specific activity of 5.52 mCi/mmol.

Reactivity of the parent amido complexes of iridium with olefins: C-NH2 bond formation versus C-H activation.

Science.gov (United States)

Mena, Inmaculada; García-Orduña, Pilar; Polo, Víctor; Lahoz, Fernando J; Casado, Miguel A; Oro, Luis A

2017-08-29

Herein we report on the different chemical reactivity displayed by two mononuclear terminal amido compounds depending on the nature of the coordinated diene. Hence, treatment of amido-bridged iridium complexes [{Ir(μ-NH 2 )(tfbb)} 3 ] (1; tfbb = tetrafluorobenzobarrelene) with dppp (dppp = bis(diphenylphosphane)propane) leads to the rupture of the amido bridges forming the mononuclear terminal amido compound [Ir(NH 2 )(dppp)(tfbb)] (3) in the first stage. On changing the reaction conditions, the formation of a C-NH 2 bond between the amido moiety and the coordinated diene is observed and a new dinuclear complex [{Ir(1,2-η 2 -4-κ-C 12 H 8 F 4 N)(dppp)} 2 (μ-dppp)] (4) has been isolated. On the contrary, the diiridium amido-bridged complex [{Ir(μ-NH 2 )(cod)} 2 ] (2; cod = 1,5-cyclooctadiene) in the presence of dppb (dppb = bis(diphenylphosphane)butane) allows the isolation of a mononuclear complex [Ir(1,2,3-η 3 -6-κ-C 8 H 10 )H(dppb)] (5), as a consequence of the extrusion of ammonia. The monitoring of the reaction of 2 with dppb (and dppp) allowed us to detect terminal amido complexes [Ir(NH 2 )(P-P)(cod)] (P-P = dppb (6), dppp (7)) in solution, as confirmed by an X-ray analysis of 7. Complex 7 was observed to evolve into hydrido species 5 at room temperature. DFT studies showed that C-H bond activation occurs through the deprotonation of one methylene fragment of the cod ligand by the highly basic terminal amido moiety instead of C-H oxidative addition to the Ir(i) center.

Complementation of biotransformations with chemical C-H oxidation: copper-catalyzed oxidation of tertiary amines in complex pharmaceuticals.

Science.gov (United States)

Genovino, Julien; Lütz, Stephan; Sames, Dalibor; Touré, B Barry

2013-08-21

The isolation, quantitation, and characterization of drug metabolites in biological fluids remain challenging. Rapid access to oxidized drugs could facilitate metabolite identification and enable early pharmacology and toxicity studies. Herein, we compared biotransformations to classical and new chemical C-H oxidation methods using oxcarbazepine, naproxen, and an early compound hit (phthalazine 1). These studies illustrated the low preparative efficacy of biotransformations and the inability of chemical methods to oxidize complex pharmaceuticals. We also disclose an aerobic catalytic protocole (CuI/air) to oxidize tertiary amines and benzylic CH's in drugs. The reaction tolerates a broad range of functionalities and displays a high level of chemoselectivity, which is not generally explained by the strength of the C-H bonds but by the individual structural chemotype. This study represents a first step toward establishing a chemical toolkit (chemotransformations) that can selectively oxidize C-H bonds in complex pharmaceuticals and rapidly deliver drug metabolites.

Rhenium-catalyzed dehydrogenative olefination of C(sp(3))-H bonds with hypervalent iodine(III) reagents.

Science.gov (United States)

Gu, Haidong; Wang, Congyang

2015-06-07

A dehydrogenative olefination of C(sp(3))-H bonds is disclosed here, by merging rhenium catalysis with an alanine-derived hypervalent iodine(III) reagent. Thus, cyclic and acyclic ethers, toluene derivatives, cycloalkanes, and nitriles are all successfully alkenylated in a regio- and stereoselective manner.

One-Step Synthesis of Cu–ZnO@C from a 1D Complex [Cu0.02Zn0.98(C8H3NO6(C12H8N2]n for Catalytic Hydroxylation of Benzene to Phenol

Directory of Open Access Journals (Sweden)

Guanghui Wang

2018-05-01

Full Text Available A novel one-dimensional bimetallic complex [Cu0.02Zn0.98(C8H3NO6(C12H8N2]n (“Complex” has been synthesized by a hydrothermal method. A Cu–ZnO@C composite was obtained by a one-step pyrolysis of Complex. Correlated with the characterization results, it is confirmed that both metallic Cu0 and ZnO nanoparticles were highly dispersed on/in the carbon substrate. This simple one-step pyrolysis method avoids the high-temperature pretreatment under H2 commonly required for preparation of such Cu–ZnO catalysts. The Cu–ZnO@C composite was tested with respect to its catalytic activities for the hydroxylation of benzene to phenol with H2O2. The results indicate that the benzene conversion, phenol yield, and phenol selectivity reached the maximum values (55.7%, 32%, and 57.5%, respectively at Complex carbonized at 600 °C, and were higher than those of the commercial mixed sample. Compared with the other candidate catalysts, the turnover frequency (TOF of our Cu–ZnO@C catalyst (117.9 mmol mol−1 s−1 can be ranked at the top. The higher catalytic activities should be due to the highly dispersed metallic Cu0 and ZnO particles as well as their synergistic interaction.

Palladium-catalysed electrophilic aromatic C-H fluorination

Science.gov (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

2018-02-01

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.

The hydrogen bond between N-H or O-H and organic fluorine: favourable yes, competitive no.

Science.gov (United States)

Taylor, Robin

2017-06-01

A study was made of X-H...F-C interactions (X = N or O) in small-molecule crystal structures. It was primarily based on 6728 structures containing X-H and C-F and no atom heavier than chlorine. Of the 28 451 C-F moieties in these structures, 1051 interact with X-H groups. However, over three-quarters of these interactions are either the weaker components of bifurcated hydrogen bonds (so likely to be incidental contacts) or occur in structures where there is a clear insufficiency of good hydrogen-bond acceptors such as oxygen, nitrogen or halide. In structures where good acceptors are entirely absent, there is about a 2 in 3 chance that a given X-H group will donate to fluorine. Viable alternatives are X-H...π hydrogen bonds (especially to electron-rich aromatics) and dihydrogen bonds. The average H...F distances of X-H...F-C interactions are significantly shorter for CR 3 F (R = C or H) and Csp 2 -F acceptors than for CRF 3 . The X-H...F angle distribution is consistent with a weak energetic preference for linearity, but that of H...F-C suggests a flat energy profile in the range 100-180°. X-H...F-C interactions are more likely when the acceptor is Csp 2 -F or CR 3 F, and when the donor is C-NH 2 . They also occur significantly more often in structures containing tertiary alcohols or solvent molecules, or with Z' > 1, i.e. when there may be unusual packing problems. It is extremely rare to find X-H...F-C interactions in structures where there are several unused good acceptors. When it does happen, there is often a clear reason, e.g. awkwardly shaped molecules whose packing isolates a donor group from the good acceptors.

Electrochemical Cobalt-Catalyzed C-H Activation.

Science.gov (United States)

Sauermann, Nicolas; Meyer, Tjark H; Ackermann, Lutz

2018-06-19

Carbon-heteroatom bonds represent omnipresent structural motifs of the vast majority of functionalized materials and bioactive compounds. C-H activation has emerged as arguably the most efficient strategy to construct C-Het bonds. Despite of major advances, these C-H transformations were largely dominated by precious transition metal catalysts, in combination with stoichiometric, toxic metal oxidants. Herein, we discuss the recent evolution of cobalt-catalyzed C-H activations that enable C-Het formations with electricity as the sole sustainable oxidant until May 2018. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

1995-01-01

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)

Si/C and H coadsorption at 4H-SiC{0001} surfaces

Energy Technology Data Exchange (ETDEWEB)

Wachowicz, E., E-mail: elwira@ifd.uni.wroc.pl [Institute of Experimental Physics, University of Wrocław, Plac M. Borna 9, PL-50-204 Wrocław (Poland); Interdisciplinary Centre for Mathematical and Computational Modelling, University of Warsaw, Pawińskiego 5a, PL-02-106 Warsaw (Poland)

2016-06-15

Highlights: • Si on C-terminated and C on Si-terminated surface adsorb in the H{sub 3} hollow site. • The preferred adsorption site is in contrary to the stacking order of bulk crystal. • The presence of hydrogen increases the adsorption energy of Si/C. • Hydrogen weakens the bonds between the adsorbed Si or C and the surface. • Carbon adsorbs on top of the surface carbon on the C-terminated surface. • With both C and H on Si-terminated surface the surface state vanishes. - Abstract: Density functional theory (DFT) study of adsorption of 0.25 monolayer of either Si or C on 4H-SiC{0001} surfaces is presented. The adsorption in high-symmetry sites on both Si- and C-terminated surfaces was examined and the influence of the preadsorbed 0.25 ML of hydrogen on the Si/C adsorption was considered. It was found out that for Si on C-terminated surface and C on Si-terminated the most favourable is threefolded adsorption site on both clean and H-precovered surface. This is contrary to the bulk crystal stacking order which would require adsorption on top of the topmost surface atom. In those cases, the presence of hydrogen weakens the bonding of the adsorbate. Carbon on the C-terminated surface, only binds on-top of the surface atom. The C−C bond-length is almost the same for the clean surface and for one with H and equals to ∼1.33 Å which is shorter by ∼0.2 than in diamond. The analysis of the electronic structure changes under adsorption is also presented.

Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

KAUST Repository

Elshewy, Ahmed M.

2013-12-01

Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.

Boron-Based Catalysts for C-C Bond-Formation Reactions.

Science.gov (United States)

Rao, Bin; Kinjo, Rei

2018-05-02

Because the construction of the C-C bond is one of the most significant reactions in organic chemistry, the development of an efficient strategy has attracted much attention throughout the synthetic community. Among various protocols to form C-C bonds, organoboron compounds are not just limited to stoichiometric reagents, but have also made great achievements as catalysts because of the easy modification of the electronic and steric impacts on the boron center. This review presents recent developments of boron-based catalysts applied in the field of C-C bond-formation reactions, which are classified into four kinds on the basis of the type of boron catalyst: 1) highly Lewis acidic borane, B(C 6 F 5 ) 3 ; 2) organoboron acids, RB(OH) 2 , and their ester derivatives; 3) borenium ions, (R 2 BL)X; and 4) other miscellaneous kinds. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selenoglutathione Diselenide: Unique Redox Reactions in the GPx-Like Catalytic Cycle and Repairing of Disulfide Bonds in Scrambled Protein.

Science.gov (United States)

Shimodaira, Shingo; Asano, Yuki; Arai, Kenta; Iwaoka, Michio

2017-10-24

Selenoglutathione (GSeH) is a selenium analogue of naturally abundant glutathione (GSH). In this study, this water-soluble small tripeptide was synthesized in a high yield (up to 98%) as an oxidized diselenide form, i.e., GSeSeG (1), by liquid-phase peptide synthesis (LPPS). Obtained 1 was applied to the investigation of the glutathione peroxidase (GPx)-like catalytic cycle. The important intermediates, i.e., GSe - and GSeSG, besides GSeO 2 H were characterized by 77 Se NMR spectroscopy. Thiol exchange of GSeSG with various thiols, such as cysteine and dithiothreitol, was found to promote the conversion to GSe - significantly. In addition, disproportionation of GSeSR to 1 and RSSR, which would be initiated by heterolytic cleavage of the Se-S bond and catalyzed by the generated selenolate, was observed. On the basis of these redox behaviors, it was proposed that the heterolytic cleavage of the Se-S bond can be facilitated by the interaction between the Se atom and an amino or aromatic group, which is present at the GPx active site. On the other hand, when a catalytic amount of 1 was reacted with scrambled 4S species of RNase A in the presence of NADPH and glutathione reductase, native protein was efficiently regenerated, suggesting a potential use of 1 to repair misfolded proteins through reduction of the non-native SS bonds.

Molecular and crystal structure of nido-9-C5H5N-11-I-7,8-C2B9H10: supramolecular architecture via hydrogen bonding X-H...I (X = B, C)

International Nuclear Information System (INIS)

Polyanskaya, T.M.

2006-01-01

A monocrystal X-ray diffraction study of a new iodine-containing cluster compound 9-(pyridine)-11-iodo-decahydro-7,8-dicarba-nido-undecaborane [9-C 5 H 5 N-11-I-7,8-C 2 B 9 H 10 ] has been performed. Crystal data: C 7 H 15 B 9 NI, M = 337.39, monoclinic, space group P2 1 /c, unit cell parameters: a=9.348(1) A, b=11.159(1) A, c=13.442(2) A, β=98.13(1) deg, V=1388.1(5) A 3 , Z=4, d calc = 1.614 g/cm 3 , T = 295 K, F(000)=648, μ=2.276 mm -1 . The structure was solved by a direct method and refined in the full-matrix anisotropic approximation (isotropic for hydrogen atoms) to final agreement factors R 1 = 0.0254, wR 2 = 0.0454 for 2437 I hkl >2σ I from 3590 measured I hkl (an Enraf-Nonius CAD-4 diffractometer, λMoK α , graphite monochromator, θ/2θ-scanning). The molecules are joined into a supramolecular assembly by hydrogen bonds X-H...I (X = B, C) [ru

Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

Science.gov (United States)

Sad, María E; Neurock, Matthew; Iglesia, Enrique

2011-12-21

This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. © 2011 American Chemical Society

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

2011-02-17

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

Catalytic mechanism of the dehydrogenation of ethylbenzene over Fe–Co/Mg(Al)O derived from hydrotalcites

KAUST Repository

Tope, Balkrishna B.; Balasamy, Rabindran J.; Khurshid, Alam; Atanda, Luqman A.; Yahiro, Hidenori; Shishido, Tetsuya; Takehira, Katsuomi; Al-Khattaf, Sulaiman S.

2011-01-01

-H+ abstraction from ethyl group on Mg2+-O2- basic sites, followed by C-O-Mg bond formation. The α-H+ abstraction by O2-(-Mg 2+) was likely followed by β-H abstraction, leading to the formations of styrene and H2. Such catalytic mechanism by the Fe 3+ acid-O2-(-Mg

Understanding of chemical bonding towards the enhancement of catalytic of Co(III)-doped ZrO2 catalyst material using x-ray photoelectron spectroscopy

International Nuclear Information System (INIS)

Nor Aziah Buang; Wan Azelee Wan Abu Bakar; Harrison, P.G.

2000-01-01

The x-ray photoelectron spectroscopy (XPS) analysis has demonstrated the formation metal ions in different oxidation states or similar oxidation state with different bonding character in the ZrO 2 based catalyst material. Interaction of cobalt oxide with ZrO 2 matrixes shows the formation of surface species of Zr-O-Co with Co in the +2 oxidation state and Co 3 O 4 -CoO in a mixture of +2 and +3 oxidation states. The formation of Zr-O-Co species in sample calcined at 400 degree C results in the more ionic character of Co-O bond and more covalent character of Zr-0 bond compared to their ordinary oxides. These behaviour cause the shifting of Co(2p) XPS peaks position towards higher binding energy and the Zr(3d) XPS peaks position towards lower binding energy. Meanwhile, the formation Of Co 3 0 4 -CoO in sample calcined at temperature of 600 degree C exhibits Co(2p) XPS peaks in the region correspond to the Co in the +2 and +3 oxidation states, which is more covalent in bonding character. The catalytic activity measurement of the catalyst material calcined at 600 o C showed that the existence of Co-O species with more covalent in bonding character gave the best catalytic performance towards 100 % conversion of carbon monoxide and propane. (Author)

Enzyme-controlled nitrogen-atom transfer enables regiodivergent C-H amination.

Science.gov (United States)

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

2014-11-05

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.

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

Science.gov (United States)

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

2018-02-16

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.

Early-transition-metal ketenimine complexes. Synthesis, reactivity, and structural characterization of complexes with. eta. sup 2 (C,N)-ketenimine groups bound to the halogenobis((trimethylsilyl)cyclopentadienyl)niobium unit. X-ray structure of Nb(. eta. sup 5 -C sub 5 H sub 4 SiMe sub 3 ) sub 2 Cl(. eta. sup 2 (C,N)-PhN double bond C double bond CPh sub 2 )

Energy Technology Data Exchange (ETDEWEB)

Antinolo, A.; Fajardo, M.; Lopez Mardomingo, C.; Otero, A. (Univ. de Alcala de Henares (Spain)); Mourad, Y.; Mugnier, Y. (Centre National de la Recherche Scientifique, Dijon (France)); Sanz-Aparicio, J.; Fonseca, I.; Florencio, F. (CSIC, Madrid (Spain))

1990-11-01

The reaction of Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}X (X = Cl, Br) with 1 equiv of various ketenimines, R{sup 1}N{double bond}C{double bond}CR{sup 2}R{sup 3}, leads to the niobium derivatives Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}X({eta}{sup 2}(C,N)-R{sup 1}N{double bond}C{double bond}CR{sup 2}R{sup 3}) (1, X = Cl, R{sup 1} = R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 2, X = Cl, R{sup 1} = p-CH{sub 3}-C{sub 6}H{sub 4}, R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 3, X = Br, R{sup 1} = R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 4, X = Br, R{sup 1} = p-CH{sub 3}-C{sub 6}H{sub 4}, R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 5, X = Cl, R{sup 1} = R{sup 2} = C{sub 6}H{sub 5}, R{sup 3} = CH{sub 3}; 6, X = Br, R{sup 1} = R{sup 2} = C{sub 6}H{sub 5}, R{sup 3} = CH{sub 3}) with the expected ketenimine C{double bond}N bonding mode. Reduction of 1 with 1 equiv of Na/Hg gives the complex Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}({eta}{sup 2}(C,N)-PhN{double bond}C{double bond}CPh{sub 2}) (9) as a paramagnetic compound. The reduction of 9 with 1 equiv of Na/Hg and the subsequent addition of a proton source (ethanol) leads to the iminoacyl compound Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}(CRNR{sup 1}) (10, R = CH(Ph{sub 2}), R{sup 1} = Ph). The one- and two-electron reductions of 1 have been studied by cyclic voltammetry experiments. The structure of 1 was determined by single-crystal X-ray diffractometry: a = 24.4904 (14) {angstrom}, b = 11.0435 (04) {angstrom}, c = 26.6130 (15) {angstrom}, {beta} = 109.890 (5){degree}, monoclinic, space group C2/c, Z = 8, V = 6,768.4 (5) {angstrom}{sup 3}, {rho}{sub calcd} = 1.3194 g/mL, R = 0.048, R{sub w} = 0.060 based on 4,806 observed reflections. The structure contains a niobium atom bonded to two cyclopentadienyl rings in a {eta}{sup 5} fashion; the coordination of the metal is completed by a Cl atom and a {eta}{sup 2}(C,N)-bonded ketenimine ligand.

Transition Metal Free C-N Bond Forming Dearomatizations and Aryl C-H Aminations by in Situ Release of a Hydroxylamine-Based Aminating Agent.

Science.gov (United States)

Farndon, Joshua J; Ma, Xiaofeng; Bower, John F

2017-10-11

We outline a simple protocol that accesses directly unprotected secondary amines by intramolecular C-N bond forming dearomatization or aryl C-H amination. The method is dependent on the generation of a potent electrophilic aminating agent released by in situ deprotection of O-Ts activated N-Boc hydroxylamines.

Superior catalytic effect of TiF3 over TiCl3 in improving the hydrogen sorption kinetics of MgH2: Catalytic role of fluorine anion

International Nuclear Information System (INIS)

Ma, L.-P.; Kang, X.-D.; Dai, H.-B.; Liang, Y.; Fang, Z.-Z.; Wang, P.-J.; Wang, P.; Cheng, H.-M.

2009-01-01

TiF 3 shows a superior catalytic effect over TiCl 3 in improving the hydrogen sorption kinetics of MgH 2 . Combined phase analysis and microstructure characterization suggest that both titanium halide additives react with host MgH 2 in a similar way. However, systematic X-ray photoelectron spectroscopy studies reveal that the incorporated fluorine (F) differs significantly from its analog chlorine (Cl) in terms of bonding state. The asymmetry of F 1s spectra and the sputtering-induced peak shift suggest that, in addition to the Mg-F bond, a new Ti-F-Mg bonding is formed in the TiF 3 -doped MgH 2 . In contrast, only one stable binding state of Cl is identified in the form of MgCl 2 for the TiCl 3 -doped MgH 2 . In combination with the designed experiments, these findings suggest that the generation of active F-containing species may be responsible for the advantage of TiF 3 over TiCl 3 in improving both the absorption and desorption kinetics of MgH 2 . Fundamentally, it emphasizes the functionality of F anion in tuning the activity of compound catalyst

Catalytic asymmetric diels-alder reaction of quinone imine ketals: a site-divergent approach.

Science.gov (United States)

Hashimoto, Takuya; Nakatsu, Hiroki; Maruoka, Keiji

2015-04-07

The catalytic asymmetric Diels-Alder reaction of quinone imine ketals with diene carbamates catalyzed by axially chiral dicarboxylic acids is reported herein. A variety of primary and secondary alkyl-substituted quinone derivatives which have not been applied in previous asymmetric quinone Diels-Alder reactions could be employed using this method. More importantly, we succeeded in developing a strategy to divert the reaction site in unsymmetrical 3-alkyl quinone imine ketals from the inherently favored unsubstituted C=C bond to the disfavored alkyl-substituted C=C bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

1H-1H correlations across N-H···N hydrogen bonds in nucleic acids

International Nuclear Information System (INIS)

Majumdar, Ananya; Gosser, Yuying; Patel, Dinshaw J.

2001-01-01

In 2H J NN -COSY experiments, which correlate protons with donor/acceptor nitrogens across N d ···HN a bonds, the receptor nitrogen needs to be assigned in order to unambiguously identify the hydrogen bond. For many situations this is a non-trivial task which is further complicated by poor dispersion of (N a ,N d ) resonances. To address these problems, we present pulse sequences to obtain direct, internucleotide correlations between protons in uniformly 13 C/ 15 N labeled nucleic acids containing N d ···HN a hydrogen bonds. Specifically, the pulse sequence H2(N1N3)H3 correlates H2(A,ω 1 ):H3(U,ω 2 ) protons across Watson-Crick A-U and mismatched G·A base pairs, the sequences H5(N3N1)H1/H6(N3N1)H1 correlate H5(C,ω 1 )/H6(C,ω 1 ):H1(G,ω 2 ) protons across Watson-Crick G-C base pairs, and the H 2 (N2N7)H8 sequence correlates NH 2 (G,A,C;ω 1 ):H8(G,A;ω 2 ) protons across G·G, A·A, sheared G·A and other mismatch pairs. These 1 H- 1 H connectivities circumvent the need for independent assignment of the donor/acceptor nitrogen and related degeneracy issues associated with poorly dispersed nitrogen resonances. The methodology is demonstrated on uniformly 13 C/ 15 N labeled samples of (a) an RNA regulatory element involving the HIV-1 TAR RNA fragment, (b) a multi-stranded DNA architecture involving a G·(C-A) triad-containing G-quadruplex and (c) a peptide-RNA complex involving an evolved peptide bound to the HIV-1 Rev response element (RRE) RNA fragment

Hydrogen bonded C-H···Y (Y = O, S, Hal) molecular complexes: A natural bond orbital analysis

Science.gov (United States)

Isaev, A. N.

2016-03-01

Hydrogen bonded C-H···Y complexes formed by H2O, H2S molecules, hydrogen halides, and halogen-ions with methane, halogen substituted methane as well as with the C2H2 and NCH molecules were studied at the MP2/aug-cc-pVDZ level. The structure of NBOs corresponding to lone pair of acceptor Y, n Y, and vacant anti-σ-bond C-H of proton donor was analyzed and estimates of second order perturbation energy E(2) characterizing donor-acceptor n Y → σ C-H * charge-transfer interaction were obtained. Computational results for complexes of methane and its halogen substituted derivatives show that for each set of analogous structures, the EnY→σ*C-H (2) energy tends to grow with an increase in the s-component percentage in the lone pair NBO of acceptor Y. Calculations for different C···Y distances show that the equilibrium geometries of complexes lie in the region where the E(2) energy is highest and it changes symbatically with the length of the covalent E-H bond when the R(C···Y) distance is varied. The performed analysis allows us to divide the hydrogen bonded complexes into two groups, depending on the pattern of overlapping for NBOs of the hydrogen bridge.

Theoretical study for pyridinium-based ionic liquid 1-ethylpyridinium trifluoroacetate: synthesis mechanism, electronic structure, and catalytic reactivity.

Science.gov (United States)

Zhu, Xueying; Cui, Peng; Zhang, Dongju; Liu, Chengbu

2011-07-28

By performing density functional theory calculations, we have studied the synthesis mechanism, electronic structure, and catalytic reactivity of a pyridinium-based ionic liquid, 1-ethylpyridinium trifluoroacetate ([epy](+)[CF(3)COO](-)). It is found that the synthesis of the pyridinium salt follows a S(N)2 mechanism. The electronic structural analyses show that multiple H bonds are generally involved in the pyridinium-based ionic liquid, which may play a decisive role for stabilizing the ionic liquid. The cation-anion interaction mainly involves electron transfer between the lone pair of the oxygen atom in the anion and the antibonding orbital of the C*-H bond (C* denotes the carbon atom at the ortho-position of nitrogen atom in the cation). This present work has also given clearly the catalytic mechanism of [epy](+)[CF(3)COO](-) toward to the Diels-Alder (D-A) reaction of acrylonitrile with 2-methyl-1,3-butadiene. Both the cation and anion are shown to play important roles in promoting the D-A reaction. The cation [epy](+), as a Lewis acid, associates the C≡N group by C≡N···H H bond to increase the polarity of the C═C double bond in acrylonitrile, while the anion CF(3)COO(-) links with the methyl group in 2-methyl-1,3-butadiene by C-H···O H bond, which weakens the electron-donating capability of methyl and thereby lowers the energy barrier of the D-A reaction. The present results are expected to provide valuable information for the design and application of pyridinium-based ionic liquids. © 2011 American Chemical Society

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

Science.gov (United States)

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

2017-12-14

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.

Solution Phase Measurement of Both Weak Sigma and C-H---X- Hydrogen Bonding Interactions in Synthetic Anion Receptors

Energy Technology Data Exchange (ETDEWEB)

Berryman, Mr. Orion B. [University of Oregon; Sather, Mr. Aaron C [University of Oregon; Hay, Benjamin [ORNL; Meisner, Mr. Jeffrey S. [University of Oregon; Johnson, Prof. Darren W. [University of Oregon

2008-01-01

A series of tripodal receptors preorganize electron-deficient aromatic rings to bind halides in organic solvents using weak sigma anion-to-arene interactions or C-H---X- hydrogen bonds. 1H NMR spectroscopy proves to be a powerful technique for quantifying binding in solution, and determining the interaction motifs, even in cases of weak binding.

Palladium Catalyzed Allylic C-H Alkylation

DEFF Research Database (Denmark)

Engelin, Casper Junker; Fristrup, Peter

2011-01-01

are highlighted with emphasis on those leading to C-C bond formation, but where it was deemed necessary for the general understanding of the process closely related C-H oxidations and aminations are also included. It is found that C-H cleavage is most likely achieved by ligand participation which could involve......-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation...... an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence...

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

2007-01-01

with participation of H+ or electrochemically produced hydrogen. When added, methane partially suppresses the electrochemical reduction of NO. Methane outlet concentration monitoring has shown the CH4 participation in the chemical catalytic reduction, i.e., methane co-adsorption with NO inhibited the electrochemical...... NO reduction and introduced a dominant chemical path of the NO reduction. The products of the NO reduction with methane were N2, C2H4, and water. The catalytic NO reduction by methane was promoted when the catalyst was negatively polarized (−0.2 V). Repeated negative polarization of the catalyst increased...

Tritium Labeled Gentamicin C: II.- Bioradiactive Degradation Products of Gentamicin by Catalytic H2O-3H Exchange Reaction; Getamicina C Tritiada: II.- Productos de Degradacion Radiactivos y Bioactivos en el Intercambio Catalitico con H2O-3H

Energy Technology Data Exchange (ETDEWEB)

Suarez, C; Diaz, A; Paz, D; Jimeno, M L

1992-07-01

The main bio radioactive degradation products from catalytic hydrogen exchange of gentamicin C, (C1 + C2 + Cla) in basic form, are generated by N-demethylation in 3{sup -}N and 6-N positions. Their structures were confirmed by 1HNMR and 13CNMR. These derivatives were fractionated by chromatography on silica gel. Antibacterial activities were similar to those of the parent antibiotics. Tritium exchange, under vacuum or nitrogen, is highly increased (4:1) when gentamicin are in basic form. In contrast with gentamicin sulfate, hydrolytic sub products as gramine, genta mines, garosamine and purpurosamines are practically absent. To properly optimize the exchange process, the composition of the gentamicin C complex must be taken into account. The exchange decreases in the order C2 > C1> Cla. Because of 6'-N-demethyl gentamicin C1 is C2, the radiochemical yield of C2 appears enhanced in the H2O-3H exchange of a mixture of them. Radioactivity distribution among the components and subunits of these three gentamicin were studied by strong and mild hydrolysis, and by methanolysis. (Author) 18 refs.

Molecular heterogeneous catalysts derived from bipyridine-based organosilica nanotubes for C-H bond activation.

Science.gov (United States)

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

2017-06-01

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.

Selective C(sp2)-C(sp) bond cleavage: the nitrogenation of alkynes to amides.

Science.gov (United States)

Qin, Chong; Feng, Peng; Ou, Yang; Shen, Tao; Wang, Teng; Jiao, Ning

2013-07-22

Breakthrough: A novel catalyzed direct highly selective C(sp2)-C(sp) bond functionalization of alkynes to amides has been developed. Nitrogenation is achieved by the highly selective C(sp2)-C(sp) bond cleavage of aryl-substituted alkynes. The oxidant-free and mild conditions and wide substrate scope make this method very practical. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A low-barrier hydrogen bond mediates antibiotic resistance in a noncanonical catalytic triad

Science.gov (United States)

2018-01-01

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

Ligand-accelerated activation of strong C-H bonds of alkanes by a (salen)ruthenium(VI)-nitrido complex.

Science.gov (United States)

Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Yiu, Shek-Man; Lau, Tai-Chu

2012-09-03

Kinetic and mechanistic studies on the intermolecular activation of strong C-H bonds of alkanes by a (salen)ruthenium(VI) nitride were performed. The initial, rate-limiting step, the hydrogen atom transfer (HAT) from the alkane to Ru(VI)≡N, generates Ru(V)=NH and RC·HCH(2)R. The following steps involve N-rebound and desaturation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ternary electrocatalysts for oxidizing ethanol to carbon dioxide: making ir capable of splitting C-C bond.

Science.gov (United States)

Li, Meng; Cullen, David A; Sasaki, Kotaro; Marinkovic, Nebojsa S; More, Karren; Adzic, Radoslav R

2013-01-09

Splitting the C-C bond is the main obstacle to electrooxidation of ethanol (EOR) to CO(2). We recently demonstrated that the ternary PtRhSnO(2) electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article, we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We characterized and compared the properties of several carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO(2) NP core decorated with multimetallic nanoislands (MM' = PtIr, PtRh, IrRh, PtIrRh) prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM'/SnO(2) NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity toward CO(2) formation of several of these MM'/SnO(2)/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO(2)/C catalysts. We demonstrate that the PtIr/SnO(2)/C catalyst with high Ir content shows outstanding catalytic properties with the most negative EOR onset potential and reasonably good selectivity toward ethanol complete oxidation to CO(2).

Directing-Group-mediated C-H-Alkynylations.

Science.gov (United States)

Caspers, Lucien D; Nachtsheim, Boris J

2018-05-18

C-C triple bonds are amongst the most versatile functional groups in synthetic chemistry. Complementary to the Sonogashira coupling the direct metal-catalyzed alkynylation of C-H bonds has emerged as a highly promising approach in recent years. To guarantee a high regioselectivity suitable directing groups (DGs) are necessary to guide the transition metal (TM) into the right place. In this Focus Review we present the current developments in DG-mediated C(sp 2 )-H and C(sp 3 )-H modifications with terminal alkynes under oxidative conditions and with electrophilic alkynylation reagents. We will discuss further modifications of the alkyne, in particular subsequent cyclizations to carbo- and heterocycles and modifications of the DG in the presence of the alkyne. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold-Catalyzed Formal C-C Bond Insertion Reaction of 2-Aryl-2-diazoesters with 1,3-Diketones.

Science.gov (United States)

Ren, Yuan-Yuan; Chen, Mo; Li, Ke; Zhu, Shou-Fei

2018-06-29

The transition-metal-catalyzed formal C-C bond insertion reaction of diazo compounds with monocarbonyl compounds is well established, but the related reaction of 1,3-diketones instead gives C-H bond insertion products. Herein, we report a protocol for a gold-catalyzed formal C-C bond insertion reaction of 2-aryl-2-diazoesters with 1,3-diketones, which provides efficient access to polycarbonyl compounds with an all-carbon quaternary center. The aryl ester moiety plays a crucial role in the unusual chemoselectivity, and the addition of a Brønsted acid to the reaction mixture improves the yield of the C-C bond insertion product. A reaction mechanism involving cyclopropanation of a gold carbenoid with an enolate and ring-opening of the resulting donor-acceptor-type cyclopropane intermediate is proposed. This mechanism differs from that of the traditional Lewis-acid-catalyzed C-C bond insertion reaction of diazo compounds with monocarbonyl compounds, which involves a rearrangement of a zwitterion intermediate as a key step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A FORMAÇÃO DE LIGAÇÕES DE HIDROGÊNIO π‧‧‧H, F‧‧‧H E C‧‧‧H NOS COMPLEXOS C2H2‧‧‧(HF, C2H2‧‧‧2(HF E C2H2‧‧‧3(HF

Directory of Open Access Journals (Sweden)

Boaz G. Oliveira

2016-04-01

Full Text Available In this work, a theoretical study on the basis of structural, vibrational, electronic and topological parameters of the C2H2‧‧‧(HF, C2H2‧‧‧2(HF and C2H2‧‧‧3(HF complexes concerning the formation of π‧‧‧H, F‧‧‧H and C‧‧‧H hydrogen bonds is presented. The main difference among these complexes is not properly the interaction strength, but the hydrogen bond type whose benchmark is ruled justly by the structure. Meanwhile, the occurrence of π‧‧‧H hydrogen bonds was unveiled in both C2H2‧‧‧(HF dimer and C2H2‧‧‧3(HF tetramer, although in latter, this interaction is stronger than C‧‧‧H of the C2H2‧‧‧2(HF trimer. However, the F‧‧‧H hydrogen bonds within the subunits of hydrofluoric acid are the strongest ones, reaching a partial covalent limit, and thereby contribute decisively to the stabilization of the tetramer structure. In line with this, the largest red-shifts were observed on the hydrofluoric acid trimer of the C2H2‧‧‧3(HF complex.

Anomalous H/D isotope effect in hydrogen bonded systems: H-bonded cyclic structures and transfers of protons

International Nuclear Information System (INIS)

Marechal, Y.

1993-01-01

The systematic H/D substitution is a precious tool to obtain information on the dynamics of H-bonds. It is particularly useful in IR spectroscopy where H-bonds are at the origin of particularly intense and specific bands and where the particularly great value for the m D /m H ratio ensures strongly marked effects. In most H-bonded systems the effects of these substitutions are normal, in the sense that they are at the origin of bands having intensities, centers (of intensity) and widths smaller in D-bonds by a factor close to √2 as compared to H-bonds. In some systems as carboxylic acid dimers, however, anomalous ratios of intensities are found upon such a substitution. Their origin is still obscure. Experimental results suggest that such anomalous ratios have much to do with the cyclic structure of these systems. It leads to stressing an important property of H-bonded cyclic structures which is that they seem necessary for having transfers of protons between molecules through H-bonds in a neutral aqueous medium (p H =7) at room temperature. The mechanism of such transfers of protons is still poorly known, but these transfers are now suspected to play a fundamental role in such widespread reactions as hydrolysis, peptide synthesis, etc... which may make them soon appear as being a crucial basic mechanism for reactivity of aqueous systems, particularly biological systems

Directed C-H Bond Oxidation of (+)-Pleuromutilin.

Science.gov (United States)

Ma, Xiaoshen; Kucera, Roman; Goethe, Olivia F; Murphy, Stephen K; Herzon, Seth B

2018-05-01

Antibiotics derived from the diterpene fungal metabolite (+)-pleuromutilin (1) are useful agents for the treatment Gram-positive infections in humans and farm animals. Pleuromutilins elicit slow rates of resistance development and minimal cross-resistance with existing antibiotics. Despite efforts aimed at producing new derivatives by semisynthesis, modification of the tricyclic core is underexplored, in part due to a limited number of functional group handles. Herein, we report methods to selectively functionalize the methyl groups of (+)-pleuromutilin (1) by hydroxyl-directed iridium-catalyzed C-H silylation, followed by Tamao-Fleming oxidation. These reactions provided access to C16, C17, and C18 monooxidized products, as well as C15/C16 and C17/C18 dioxidized products. Four new functionalized derivatives were prepared from the protected C17 oxidation product. C6 carboxylic acid, aldehyde, and normethyl derivatives were prepared from the C16 oxidation product. Many of these sequences were executed on gram scales. The efficiency and practicality of these routes provides an easy method to rapidly interrogate structure-activity relationships that were previously beyond reach. This study will inform the design of fully synthetic approaches to novel pleuromutilins and underscores the power of the hydroxyl-directed iridium-catalyzed C-H silylation reaction.

Tritium Labeled Gentamicin C: II.- Bioradiactive Degradation Products of Gentamicin by Catalytic H2O-3H Exchange Reaction; Getamicina C Tritiada: II.- Productos de Degradacion Radiactivos y Bioactivos en el Intercambio Catalitico con H2O-3H

Energy Technology Data Exchange (ETDEWEB)

Suarez, C.; Diaz, A.; Paz, D.; Jimeno, M. L.

1992-07-01

The main bio radioactive degradation products from catalytic hydrogen exchange of gentamicin C, (C1 + C2 + Cla) in basic form, are generated by N-demethylation in 3{sup -}N and 6-N positions. Their structures were confirmed by 1HNMR and 13CNMR. These derivatives were fractionated by chromatography on silica gel. Antibacterial activities were similar to those of the parent antibiotics. Tritium exchange, under vacuum or nitrogen, is highly increased (4:1) when gentamicin are in basic form. In contrast with gentamicin sulfate, hydrolytic sub products as gramine, genta mines, garosamine and purpurosamines are practically absent. To properly optimize the exchange process, the composition of the gentamicin C complex must be taken into account. The exchange decreases in the order C2 > C1> Cla. Because of 6'-N-demethyl gentamicin C1 is C2, the radiochemical yield of C2 appears enhanced in the H2O-3H exchange of a mixture of them. Radioactivity distribution among the components and subunits of these three gentamicin were studied by strong and mild hydrolysis, and by methanolysis. (Author) 18 refs.

Temperature-dependent transitions between normal and inverse isotope effects pertaining to the interaction of H-H and C-H bonds with transition metal centers.

Science.gov (United States)

Parkin, Gerard

2009-02-17

Deuterium kinetic isotope effects (KIEs) serve as versatile tools to infer details about reaction mechanisms and the nature of transition states, while equilibrium isotope effects (EIEs) associated with the site preferences of hydrogen and deuterium enable researchers to study aspects of molecular structure. Researchers typically interpret primary deuterium isotope effects based on two simple guidelines: (i) the KIE for an elementary reaction is normal (k(H)/k(D) > 1) and (ii) the EIE is dictated by deuterium preferring to be located in the site corresponding to the highest frequency oscillator. In this Account, we evaluate the applicability of these rules to the interactions of H-H and C-H bonds with a transition metal center. Significantly, experimental and computational studies question the predictability of primary EIEs in these systems based on the notion that deuterium prefers to occupy the highest frequency oscillator. In particular, the EIEs for (i) formation of sigma-complexes by coordination of H-H and C-H bonds and (ii) oxidative addition of dihydrogen exhibit unusual temperature dependencies, such that the same system may demonstrate both normal (i.e., K(H)/K(D) > 1) and inverse (i.e., K(H)/K(D) ZPE (where SYM is the symmetry factor, MMI is the mass-moment of inertia term, EXC is the excitation term, and ZPE is the zero-point energy term), and the distinctive temperature profile results from the inverse ZPE (enthalpy) and normal [SYM x MMI x EXC] (entropy) components opposing each other and having different temperature dependencies. At low temperatures, the ZPE component dominates and the EIE is inverse, while at high temperatures, the [SYM x MMI x EXC] component dominates and the EIE is normal. The inverse nature of the ZPE term is a consequence of the rotational and translational degrees of freedom of RH (R = H, CH(3)) becoming low-energy isotopically sensitive vibrations in the product, while the normal nature of the [SYM x MMI x EXC] component

Catalytic mechanism of the dehydrogenation of ethylbenzene over Fe–Co/Mg(Al)O derived from hydrotalcites

KAUST Repository

Tope, Balkrishna B.

2011-11-01

Catalytic mechanism of ethylbenzene dehydrogenation over Fe-Co/Mg(Al)O derived from hydrotalcites has been studied based on the XAFS and XPS catalyst characterization and the FTIR measurements of adsorbed species. Fe-Co/Mg(Al)O showed synergy, whereas Fe-Ni/Mg(Al)O showed no synergy, in the dehydrogenation of ethylbenzene. Ni species were stably incorporated as Ni2+ in the regular sites in periclase and spinel structure in the Fe-Ni/Mg(Al)O. Contrarily, Co species exists as a mixture of Co3+/Co2+ in the Fe-Co/Mg(Al)O and was partially isolated from the regular sites in the structures with increasing the Co content. Co addition enhanced Lewis acidity of Fe3+ active sites by forming Fe3+-O-Co 3+/2+(1/1) bond, resulting in an increase in the activity. FTIR of ethylbenzene adsorbed on the Fe-Co/Mg(Al)O clearly showed formations of C-O bond and π-adsorbed aromatic ring. This suggests that ethylbenzene was strongly adsorbed on the Fe3+ acid sites via π-bonding and the dehydrogenation was initiated by α-H+ abstraction from ethyl group on Mg2+-O2- basic sites, followed by C-O-Mg bond formation. The α-H+ abstraction by O2-(-Mg 2+) was likely followed by β-H abstraction, leading to the formations of styrene and H2. Such catalytic mechanism by the Fe 3+ acid-O2-(-Mg2+) base couple and the Fe 3+/Fe2+ reduction-oxidation cycle was further assisted by Co3+/Co2+, leading to a good catalytic activity for the dehydrogenation of ethylbenzene. © 2011 Elsevier B.V. All rights reserved.

Formation of a dinuclear copper(II) complex through the cleavage of CBond' name='Single-Bond' value='Single-Bond'/>N bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

Energy Technology Data Exchange (ETDEWEB)

Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M. [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor (Malaysia); Kassim, Mohammad B. [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor, Malaysia and Fuel Cell Institute, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor (Malaysia)

2014-09-03

A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-(3-(pyridin-2-yl)-pyrazolato) and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the C{sub benzoyl}Bond' name='Single-Bond' value='Single-Bond'/>N bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the (3-(pyridin-2-yl)-pyrazolato)(3-(pyridin-2-yl)-1H-pyrazole)Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ε = 116 dm{sup 3} mol{sup −1} cm{sup −1}) supports the presence of Cu(II) centres.

Catalytic conversion of 11C-labeled methanol over Cs-ZSM-5 zeolite

International Nuclear Information System (INIS)

Sarkadi-Priboczki, E.; Kovacs, Z.; Kumar, N.; Salmi, T.; Murzin, D.Yu.

2004-01-01

Reaction mechanism of the conversion of 11 C labeled methanol over basic Cs-ZSM-5 zeolite catalyst was investigated and the reaction products obtained were compared with that of H-ZSM-5 acidic catalyst. The catalytic experiments were carried out by passing 11 C-labeled methanol with He as a carrier gas over Cs-ZSM-5 packed in a micro reactor. After adsorption of the radio methanol, the catalyst was heated up to 330 deg C. The products of the catalytic conversion of the 11 C-labeled methanol were analyzed by radio-gas chromatography (gas chromatograph with thermal conductivity detector on-line coupled with a radioactivity detector). (N.T.)

What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [(H)2Cl(PMe3)2M(σ-H-BR)] (M = Fe, Ru, Os).

Science.gov (United States)

Pandey, Krishna K

2012-03-21

Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron, ruthenium and osmium [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe(2), Ph) at the BP86/TZ2P/ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [(H)(2)Cl(PMe(3))(2)Ru(HBNMe(2))], [(H)(2)Cl(PMe(3))(2)Os(HBR)] (R = OMe, NMe(2)) are in excellent agreement with structurally characterized complexes [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))], [(H)(2)Cl(P(i)Pr(3))(2)Os{σ-H-BOCH(2)CH(2)OB(O(2)CH(2)CH(2))}] and [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))]. The longer calculated M-B bond distance in complex [(H)(2)Cl(PMe(3))(2)M(σ-H-BNMe(2))] are due to greater B-N π bonding and as a result, a weaker M-B π-back-bonding. The B-H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B-H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M-(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M-σ-H-BR interactions in the complexes [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] is the interaction between neutral fragments [(H)(2)Cl(PMe(3))(2)M] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M-σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the ΔE(prep) values, it is clearly the most appropriate choice of

Rhenium-Promoted C-C Bond-Cleavage Reactions of Internal Propargyl Alcohols.

Science.gov (United States)

Lee, Kui Fun; Bai, Wei; Sung, Herman H Y; Williams, Ian D; Lin, Zhenyang; Jia, Guochen

2018-06-07

The first examples of C-C bond cleavage reactions of internal propargyl alcohols to give vinylidene complexes are described. Treatment of [Re(dppm) 3 ]I with RC≡CC(OH)R'R'' (R=aryl, alkyl; C(OH)R'R''=C(OH)Ph 2, C(OH)Me 2 , C(OH)HPh, C(OH)H 2 ) produced the vinylidene complexes ReI(=C=CHR)(dppm) 2 with the elimination of C(O)R'R''. Computational studies support that the reactions proceed through a β-alkynyl elimination of alkoxide intermediates Re{OC(R')(R'')C≡CR}(dppm) 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic Hydroaminoalkylation Reactions

KAUST Repository

Hamzaoui, Bilel

2015-09-25

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.

Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic Hydroaminoalkylation Reactions

KAUST Repository

Hamzaoui, Bilel; Pelletier, Jé ré mie D. A.; El Eter, Mohamad; Chen, Yin; Abou-Hamad, Edy; Basset, Jean-Marie

2015-01-01

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.

A new face of phenalenyl-based radicals in the transition metal-free C-H arylation of heteroarenes at room temperature: trapping the radical initiator via C-C σ-bond formation.

Science.gov (United States)

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

2017-11-01

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.

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.

2004-11-27

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.

TEMPO functionalized C60 fullerene deposited on gold surface for catalytic oxidation of selected alcohols

International Nuclear Information System (INIS)

Piotrowski, Piotr; Pawłowska, Joanna; Sadło, Jarosław Grzegorz; Bilewicz, Renata; Kaim, Andrzej

2017-01-01

C 60 TEMPO 10 catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C 60 TEMPO 10 @Au composite catalyst had a particle size of 0.5–0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79–98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O 2 /Fe 3+ system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.

Friedel-Crafts reaction of benzyl fluorides: selective activation of C-F bonds as enabled by hydrogen bonding.

Science.gov (United States)

Champagne, Pier Alexandre; Benhassine, Yasmine; Desroches, Justine; Paquin, Jean-François

2014-12-08

A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diffusion bonding of reduced activation ferritic steel F82H for demo blanket application

International Nuclear Information System (INIS)

Kurasawa, T.; Tamura, M.

1996-01-01

A reduced activation ferritic steel, a grade F82H developed by JAERI, is a promising candidate structural material for the blanket and the first wall of DEMO reactors. In the present study, diffusion bonding of F82H has been investigated to develop the fabrication procedures of the blanket box and the first wall panel with cooling channels embedded by F82H. The parameters examined are the bonding temperature (810-1050 C), bonding pressure (2-10 MPa) and roughness of the bonding surface (0.5-12.8 μR max ), and metallurgical examination and mechanical tests of the diffusion bonded joints have been conducted. From the tests, sufficient bonding was obtained under the temperatures of 840-1 050 C (compressive stress of 3-12 MPa), and it was found that heat treatment following diffusion bonding is essential to obtain the mechanical properties similar to that of the base metal. (orig.)

B-H Bond Activation by an Amidinate-Stabilized Amidosilylene: Non-Innocent Amidinate Ligand.

Science.gov (United States)

Khoo, Sabrina; Shan, Yu-Liang; Yang, Ming-Chung; Li, Yongxin; Su, Ming-Der; So, Cheuk-Wai

2018-05-21

The activation of B-H and B-Cl bonds in boranes by base-stabilized low-valent silicon compounds is described. The reaction of the amidinato amidosilylene-borane adduct [L{Ar(Me 3 Si)N}SiBH 3 ] [1; L = PhC(N tBu) 2 , and Ar = 2,6- iPr 2 C 6 H 3 ] with MeOTf in toluene at room temperature formed [L{Ar(Me 3 Si)N}SiBH 2 OTf] (2). [LSiN(SiMe 3 )Ar] in compound 2 then underwent a B-H bond activation with BH 2 OTf in refluxing toluene to afford the B-H bond activation product [LB(H)Si(H)(OTf){N(SiMe 3 )Ar}] (3). On the other hand, when compound 2 was reacted with 4-dimethylaminopyridine in refluxing toluene, another B-H bond activation product [(μ-κ1:κ1-L)B(H)(DMAP)Si(H){N(Ar)SiMe 3 }]OTf (4) was afforded. Mechanistic studies show that "(μ-κ1:κ1-L)B(H)(OTf)Si(H){N(Ar)SiMe 3 }" (2A) is the key intermediate in the reactions mentioned above. The formation of 2A is further evidenced by the activation of the B-Cl bond in PhBCl 2 by the amidinato silicon(I) dimer [LSi:] 2 to form the B-Cl bond activation product [(μ-κ1:κ1-L)B(Cl)(Ph)Si(Cl)] 2 (6). Compounds 2-4 and 6 were characterized by nuclear magnetic resonance spectroscopy and X-ray crystallography.

Rational Design of Disulfide Bonds Increases Thermostability of a Mesophilic 1,3-1,4-β-Glucanase from Bacillus terquilensis.

Directory of Open Access Journals (Sweden)

Chengtuo Niu

Full Text Available 1,3-1,4-β-glucanase is an important biocatalyst in brewing industry and animal feed industry, while its low thermostability often reduces its application performance. In this study, the thermostability of a mesophilic β-glucanase from Bacillus terquilensis was enhanced by rational design and engineering of disulfide bonds in the protein structure. Protein spatial configuration was analyzed to pre-exclude the residues pairs which negatively conflicted with the protein structure and ensure the contact of catalytic center. The changes in protein overall and local flexibility among the wild-type enzyme and the designated mutants were predicted to select the potential disulfide bonds for enhancement of thermostability. Two residue pairs (N31C-T187C and P102C-N125C were chosen as engineering targets and both of them were proved to significantly enhance the protein thermostability. After combinational mutagenesis, the double mutant N31C-T187C/P102C-N125C showed a 48.3% increase in half-life value at 60°C and a 4.1°C rise in melting temperature (Tm compared to wild-type enzyme. The catalytic property of N31C-T187C/P102C-N125C mutant was similar to that of wild-type enzyme. Interestingly, the optimal pH of double mutant was shifted from pH6.5 to pH6.0, which could also increase its industrial application. By comparison with mutants with single-Cys substitutions, the introduction of disulfide bonds and the induced new hydrogen bonds were proved to result in both local and overall rigidification and should be responsible for the improved thermostability. Therefore, the introduction of disulfide bonds for thermostability improvement could be rationally and highly-effectively designed by combination with spatial configuration analysis and molecular dynamics simulation.

Catalytic conversion of ethanol on H-Y zeolite

Directory of Open Access Journals (Sweden)

Čegar Nedeljko

2005-01-01

Full Text Available The catalytic activity of the H-form of synthetic zeolite NaY was examined in this study. The catalytic activity was determined according to the rate of ethanol conversion in a gas phase in the static system. In the conversion of ethanol on synthetic NaY zeolite at 585, 595, and 610 K, on which the reaction develops at an optimal rate, ethene and diethyl ether are evolved in approximately the same quantity. After transforming the NaY zeolite into the H-form, its catalytic activity was extremely increases so, the reaction develops at a significantly lower temperature with a very large increase in the reaction rate. The distribution of the products also changes, so that at lower temperatures diethyl ether is elvolved in most cases, and the development of ethene is favored at higher ones, and after a certain period of time there is almost complete conversion of ethanol into ethene. The increase in catalytic activity, as well as the change of selectivity of conversion of ethanol on the H-form of zeolite, is the result of removing Na+ cations in the NaY zeolite, so that more acidic catalyst is obtained which contains a number of acidic catalytically active centers, as well as a more powerful one compared to the original NaY zeolite.

Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C-H Bond Activation.

Science.gov (United States)

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

2015-08-21

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.

Solitons on H bonds in proteins

DEFF Research Database (Denmark)

d'Ovidio, F.; Bohr, H.G.; Lindgård, Per-Anker

2003-01-01

system shows that the solitons are spontaneously created and are stable and moving along the helix axis. A perturbation on one of the three H-bond lines forms solitons on the other H bonds as well. The robust solitary wave may explain very long-lived modes in the frequency range of 100 cm(-1) which...... are found in recent x-ray laser experiments. The dynamics parameters of the Toda lattice are in accordance with the usual Lennard-Jones parameters used for realistic H-bond potentials in proteins....

Superior catalytic effect of TiF{sub 3} over TiCl{sub 3} in improving the hydrogen sorption kinetics of MgH{sub 2}: Catalytic role of fluorine anion

Energy Technology Data Exchange (ETDEWEB)

Ma, L.-P.; Kang, X.-D.; Dai, H.-B.; Liang, Y.; Fang, Z.-Z.; Wang, P.-J. [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China); Wang, P. [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China)], E-mail: pingwang@imr.ac.cn; Cheng, H.-M. [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China)

2009-04-15

TiF{sub 3} shows a superior catalytic effect over TiCl{sub 3} in improving the hydrogen sorption kinetics of MgH{sub 2}. Combined phase analysis and microstructure characterization suggest that both titanium halide additives react with host MgH{sub 2} in a similar way. However, systematic X-ray photoelectron spectroscopy studies reveal that the incorporated fluorine (F) differs significantly from its analog chlorine (Cl) in terms of bonding state. The asymmetry of F 1s spectra and the sputtering-induced peak shift suggest that, in addition to the Mg-F bond, a new Ti-F-Mg bonding is formed in the TiF{sub 3}-doped MgH{sub 2}. In contrast, only one stable binding state of Cl is identified in the form of MgCl{sub 2} for the TiCl{sub 3}-doped MgH{sub 2}. In combination with the designed experiments, these findings suggest that the generation of active F-containing species may be responsible for the advantage of TiF{sub 3} over TiCl{sub 3} in improving both the absorption and desorption kinetics of MgH{sub 2}. Fundamentally, it emphasizes the functionality of F anion in tuning the activity of compound catalyst.

Three closely related 4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridines: synthesis, molecular conformations and hydrogen bonding in zero, one and two dimensions.

Science.gov (United States)

Sagar, Belakavadi K; Harsha, Kachigere B; Yathirajan, Hemmige S; Rangappa, Kanchugarakoppal S; Rathore, Ravindranath S; Glidewell, Christopher

2017-03-01

In each of 1-(4-fluorophenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine, C 21 H 19 F 4 N 3 O 2 S, (I), 1-(4-chlorophenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine, C 21 H 19 ClF 3 N 3 O 2 S, (II), and 1-(3-methylphenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine, C 22 H 22 F 3 N 3 O 2 S, (III), the reduced pyridine ring adopts a half-chair conformation with the methylsulfonyl substituent occupying an equatorial site. Although compounds (I) and (II) are not isostructural, having the space groups Pbca and P2 1 2 1 2 1 , respectively, their molecular conformations are very similar, but the conformation of compound (III) differs from those of (I) and (II) in the relative orientation of the N-benzyl and methylsulfonyl substituents. In compounds (II) and (III), but not in (I), the trifluoromethyl groups are disordered over two sets of atomic sites. Molecules of (I) are linked into centrosymmetric dimers by C-H...π(arene) hydrogen bonds, molecules of (II) are linked by two C-H...O hydrogen bonds to form ribbons of R 3 3 (18) rings, which are themselves further linked by a C-Cl...π(arene) interaction, and a combination of C-H...O and C-H...π(arene) hydrogen bonds links the molecules of (III) into sheets. Comparisons are made with the structures of some related compounds.

Synthesis of Co/N-HNTs composites and investigation on its catalytic activity for H2 generation

International Nuclear Information System (INIS)

Zhao, Dongcui; Cheng, Zhilin; Nan, Zhaodong

2016-01-01

Co/N-HNTs composites were synthesized via a one-pot solvothermal method, where amine functional halloysite nanotubes (N-HNTs) were used as support materials. Effects of sulfosuccinate sodium salt (AOT), an anionic surfactant, on morphology and dispersibility of Co particles anchored at the N-HNTs were studied. The dispersibility of the Co particles was promoted with the increase of the AOT concentration. The as-obtained composite was used as a catalyst to generate H 2 gas by hydrolysis of NaBH 4 solution. The catalytic activity of the composite was significantly enhanced than the pure Co and Co/graphene composite at the same experimental conditions reported by our laboratory, and the catalyst was conveniently separated from the solution by a magnet. The catalytic activity was enhanced when the dispersibility of the Co particles was improved at the surface of the N-HNTs and the Co content contained in the composite was lowed. At the same time, the Co particles anchored at the inner surface of the N-HNTs resulted in higher catalytic activity, where the Co particles may bond with nitrogen atoms. The activation energy for the hydrolysis of NaBH 4 was calculated to be about 15.42 kJ mol −1 . The catalyst can be continuously used for four times with about the same catalytic activity. - Highlights: • Co/N-HNTs composites are synthesized. • The dispersibility and morphology of the Co particles anchored at the N-HNTs are modified by AOT. • The composite shows higher catalytic activity for production H 2 gas.

Structural insights into the loss of catalytic competence in pectate lyase activity at low pH

DEFF Research Database (Denmark)

Ali, Salyha; Søndergaard, Chresten Rauff; Teixeira, Susana

2015-01-01

at the active centre (+1 subsite), they withdraw electrons acidifying the C5 proton facilitating its abstraction by the catalytic arginine. Here we show that activity is lost at low pH because protonation of aspartates results in the loss of the two catalytic calcium-ions causing a profound failure to correctly...

Theoretical Prediction on [5]Radialene Sandwich Complexes (CpM)2(C10H10) (Cp = η5-C5H5; M = Fe, Co, Ni): Geometry, Spin States, and Bonding.

Science.gov (United States)

Liu, Nan-Nan; Xue, Ying-Ying; Ding, Yi-Hong

2017-02-09

[5]Radialene, the missing link for synthesis of radialene family, has been finally obtained via the preparation and decomplexation of the [5]radialene-bis-Fe(CO) 3 complex. The stability of [5]radialene complex benefits from the coordination with Fe(CO) 3 by losing free 1,3-butadiene structures to avoid polymerization. In light of the similar coordination ability of half-sandwiches CpM(Cp = η 5 -C 5 H 5 ; M = Fe, Co, Ni), there is a great possibility that the sandwiched complexes of [5]radialene with CpM are available. Herein, we present the first theoretical prediction on the geometry, spin states and bonding of (CpM)(C 10 H 10 ) and (CpM) 2 (C 10 H 10 ). For M = Fe, Co, Ni, the ground states of (CpM)(C 10 H 10 ) and (CpM) 2 (C 10 H 10 ) are doublet and triplet, singlet and singlet, and doublet and triplet states, where each Fe, Co, and Ni adopts 17, 18, and 19 electron-configuration, respectively. In particular, (CpFe) 2 (C 10 H 10 ) and (CpNi) 2 (C 10 H 10 ) have considerable open-shell singlet features. Generally the trans isomers of (CpM) 2 (C 10 H 10 ) with two CpM fragments on the opposite sides of the [5]radialene plane are apparently more stable than the cis ones with CpM fragments on the same side. However, for the singlet and triplet isomers of (CpNi) 2 (C 10 H 10 ) (both cis and trans isomers), the energy differences are relatively small, indicating that these isomers all have the opportunity to exist. Besides, the easy Diels-Alder (DA) dimerization between the [3]dendralene-like fragments of (CpM)(C 10 H 10 ) suggests the great difficulty in isolating the (CpM)(C 10 H 10 ) monomer.

Stepwise Ti-Cl, Ti-CH3, and Ti-C6H5 bond dissociation enthalpies in bis(pentamethylcyclopentadienyl)titanium complexes

NARCIS (Netherlands)

Dias, Alberto R.; Salema, Margarida S.; Martinho Simões, Jose A.; Pattiasina, Johannes W.; Teuben, Jan H.

1988-01-01

Reaction-solution calorimetric studies involving the complexes Ti[η5-C5(CH3)5]2(CH3)2, Ti[η5-C5(CH3)5]2(CH3), Ti[η5-C5(CH3)5]2(C6H5), Ti[η5-C5(CH3)5]2Cl2, and Ti[η5-C5(CH3)5]2Cl, have enabled derivation of titanium-carbon and titanium-chlorine stepwise bond dissociation enthalpies in these species.

Pd-Catalyzed Acetoxylation of γ-C(sp3)-H Bonds of Amines Directed by a Removable Bts-Protecting Group.

Science.gov (United States)

Zheng, Yong; Song, Weibin; Zhu, Yefu; Wei, Bole; Xuan, Lijiang

2018-02-16

Pd-catalyzed acetoxylation of γ-C(sp 3 )-H bonds directed by Bts-protected amines using inexpensive PhI(OAc) 2 as oxidant is reported. The Bts-protecting group is easily introduced and removed under mild conditions. This protocol provides an important strategy for the construction of γ-hydroxyl amine derivatives.

Size and Site Dependence of the Catalytic Activity of Iridium Clusters toward Ethane Dehydrogenation.

Science.gov (United States)

Ge, Yingbin; Jiang, Hao; Kato, Russell; Gummagatta, Prasuna

2016-12-01

This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Ir n (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-ζ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Ir n + C 2 H 6 → H-Ir n -C 2 H 5 → (H) 2 -Ir n -C 2 H 4 , the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir 8 is the least reactive toward H-elimination in ethane: Ir 8 + C 2 H 6 → H-Ir 8 -C 2 H 5 has a large (65 kJ/mol) energy barrier, whereas Ir 12 (3 × 2 × 2 cuboid) and Ir 18 (3 × 3 × 2 cuboid) lower this energy barrier to 22 and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir 18 + C 2 H 6 → H-Ir 18 -C 2 H 5 reaction is 3, 48, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir 18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C-H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Ir n + C 2 H 6 + 1 / 2 O 2 → Ir n + C 2 H 4 + H 2 O. These results will be useful toward reducing the energy cost of ethane dehydrogenation in industry.

Cleavage of thymine N3-H bonds by low-energy electrons attached to base π* orbitals

International Nuclear Information System (INIS)

Theodore, Magali; Sobczyk, Monika; Simons, Jack

2006-01-01

In this work, we extend our earlier studies on single strand break (SSB) formation in DNA to consider the possibility of cleaving a thymine N 3 -H bond to generate a nitrogen-centered anion and a hydrogen radical which might proceed to induce further bond cleavages. In earlier studies, we considered SSBs induced by low-energy electrons that attach to DNA bases' π* orbitals or to phosphate P=O π* orbitals to cleave sugar-phosphate C-O bonds or base-sugar N 1 -C bonds. We also studied the effects of base π-stacking on the rates of such bond cleavages. To date, our results suggest that sugar-phosphate C-O bonds have the lowest barriers to cleavage, that attachment of electrons with energies below 2 eV most likely occurs at the base π* orbitals, that electrons with energy above 2 eV can also attach to phosphate P=O π* orbitals, and that base π stacking has a modest but slowing effect on the rates of SSB formation. However, we had not yet examined the possibility that base N 3 -H bonds could rupture subsequent to base π* orbital capture. In the present work, the latter possibility is considered and it is found that the barrier to cleavage of the N 3 -H bond in thymine is considerably higher than for cleaving sugar-phosphate C-O bonds, so our prediction that SSB formation is dominated by C-O bond cleavage remains intact

Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry.

Science.gov (United States)

Klankermayer, Jürgen; Wesselbaum, Sebastian; Beydoun, Kassem; Leitner, Walter

2016-06-20

The present Review highlights the challenges and opportunities when using the combination CO2 /H2 as a C1 synthon in catalytic reactions and processes. The transformations are classified according to the reduction level and the bond-forming processes, covering the value chain from high volume basic chemicals to complex molecules, including biologically active substances. Whereas some of these concepts can facilitate the transition of the energy system by harvesting renewable energy into chemical products, others provide options to reduce the environmental impact of chemical production already in today's petrochemical-based industry. Interdisciplinary fundamental research from chemists and chemical engineers can make important contributions to sustainable development at the interface of the energetic and chemical value chain. The present Review invites the reader to enjoy this exciting area of "catalytic chess" and maybe even to start playing some games in her or his laboratory. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid-Phase Catalytic Transfer Hydrogenation of Furfural over Homogeneous Lewis Acid-Ru/C Catalysts.

Science.gov (United States)

Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G

2015-06-22

The catalytic performance of homogeneous Lewis acid catalysts and their interaction with Ru/C catalyst are studied in the catalytic transfer hydrogenation of furfural by using 2-propanol as a solvent and hydrogen donor. We find that Lewis acid catalysts hydrogenate the furfural to furfuryl alcohol, which is then etherified with 2-propanol. The catalytic activity is correlated with an empirical scale of Lewis acid strength and exhibits a volcano behavior. Lanthanides are the most active, with DyCl3 giving complete furfural conversion and a 97 % yield of furfuryl alcohol at 180 °C after 3 h. The combination of Lewis acid and Ru/C catalysts results in synergy for the stronger Lewis acid catalysts, with a significant increase in the furfural conversion and methyl furan yield. Optimum results are obtained by using Ru/C combined with VCl3 , AlCl3 , SnCl4 , YbCl3 , and RuCl3 . Our results indicate that the combination of Lewis acid/metal catalysts is a general strategy for performing tandem reactions in the upgrade of furans. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trends in Strong Chemical Bonding in C2, CN, CN-, CO, N2, NO, NO+, and O2

DEFF Research Database (Denmark)

Kepp, Kasper Planeta

2017-01-01

The strong chemical bonds between C, N, and O play a central role in chemistry, and their formation and cleavage are critical steps in very many catalytic processes. The close-lying molecular orbital energies and large correlation effects pose a challenge to electronic structure calculations and ...

Substrate-Mediated C-C and C-H Coupling after Dehalogenation.

Science.gov (United States)

Kong, Huihui; Yang, Sha; Gao, Hongying; Timmer, Alexander; Hill, Jonathan P; Díaz Arado, Oscar; Mönig, Harry; Huang, Xinyan; Tang, Qin; Ji, Qingmin; Liu, Wei; Fuchs, Harald

2017-03-15

Intermolecular C-C coupling after cleavage of C-X (mostly, X = Br or I) bonds has been extensively studied for facilitating the synthesis of polymeric nanostructures. However, the accidental appearance of C-H coupling at the terminal carbon atoms would limit the successive extension of covalent polymers. To our knowledge, the selective C-H coupling after dehalogenation has not so far been reported, which may illuminate another interesting field of chemical synthesis on surfaces besides in situ fabrication of polymers, i.e., synthesis of novel organic molecules. By combining STM imaging, XPS analysis, and DFT calculations, we have achieved predominant C-C coupling on Au(111) and more interestingly selective C-H coupling on Ag(111), which in turn leads to selective synthesis of polymeric chains or new organic molecules.

Alcohols as alkylating agents in heteroarene C-H functionalization

Science.gov (United States)

Jin, Jian; MacMillan, David W. C.

2015-09-01

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.

Alcohols as alkylating agents in heteroarene C-H functionalization.

Science.gov (United States)

Jin, Jian; MacMillan, David W C

2015-09-03

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.

Reductive Elimination Leading to C-C Bond Formation in Gold(III) Complexes: A Mechanistic and Computational Study.

Science.gov (United States)

Rocchigiani, Luca; Fernandez-Cestau, Julio; Budzelaar, Peter H M; Bochmann, Manfred

2018-06-21

The factors affecting the rates of reductive C-C cross-coupling reactions in gold(III) aryls were studied by using complexes that allow easy access to a series of electronically modified aryl ligands, as well as to gold methyl and vinyl complexes, by using the pincer compounds [(C^N^C)AuR] (R=C 6 F 5 , CH=CMe 2 , Me and p-C 6 H 4 X, where X=OMe, F, H, tBu, Cl, CF 3 , or NO 2 ) as starting materials (C^N^C=2,6-(4'-tBuC 6 H 3 ) 2 pyridine dianion). Protodeauration followed by addition of one equivalent SMe 2 leads to the quantitative generation of the thioether complexes [(C^N-CH)AuR(SMe 2 )] + . Upon addition of a second SMe 2 pyridine is displaced, which triggers the reductive aryl-R elimination. The rates for these cross-couplings increase in the sequence k(vinyl)>k(aryl)≫k(C 6 F 5 )>k(Me). Vinyl-aryl coupling is particularly fast, 1.15×10 -3  L mol -1  s -1 at 221 K, whereas both C 6 F 5 and Me couplings encountered higher barriers for the C-C bond forming step. The use of P(p-tol) 3 in place of SMe 2 greatly accelerates the C-C couplings. Computational modelling shows that in the C^N-bonded compounds displacement of N by a donor L is required before the aryl ligands can adopt a conformation suitable for C-C bond formation, so that elimination takes place from a four-coordinate intermediate. The C-C bond formation is the rate-limiting step. In the non-chelating case, reductive C(sp 2 )-C(sp 2 ) elimination from three-coordinate ions [(Ar 1 )(Ar 2 )AuL] + is almost barrier-free, particularly if L=phosphine. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic Liquefaction of Humin Substances from Sugar Biorefineries with Pt/C in 2-Propanol

NARCIS (Netherlands)

Wang, Y.; Agarwal, S.; Heeres, H. J.

The catalytic liquefaction of humins, the solid byproduct from the conversion of C6 sugars (glucose, fructose) to S-hydroxymethylfurfural (HMF) and levulinic acid (LA), using a supported Pt/C catalyst in isopropanol (IPA) as the solvent was investigated. At bench mark conditions (400 degrees C, 7 h,

Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: general strategy for amide N-C bond activation.

Science.gov (United States)

Meng, Guangrong; Szostak, Michal

2016-06-15

The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined ().

Why Does Alkylation of the N–H Functionality within M/NH Bifunctional Noyori-Type Catalysts Lead to Turnover?

International Nuclear Information System (INIS)

Dub, Pavel; Gordon, John Cameron; Scott, Brian Lindley

2017-01-01

Molecular metal/NH bifunctional Noyori-type catalysts are remarkable in that they are among the most efficient artificial catalysts developed to date for the hydrogenation of carbonyl functionalities (loadings up to ~10 –5 mol %). In addition, these catalysts typically exhibit high C=O/C=C chemo- and enantioselectivities. This unique set of properties is traditionally associated with the operation of an unconventional mechanism for homogeneous catalysts in which the chelating ligand plays a key role in facilitating the catalytic reaction and enabling the aforementioned selectivities by delivering/accepting a proton (H + ) via its N–H bond cleavage/formation. A recently revised mechanism of the Noyori hydrogenation reaction (Dub, P. A. et al. J. Am. Chem. Soc. 2014, 136, 3505) suggests that the N–H bond is not cleaved but serves to stabilize the turnover-determining transition states (TDTSs) via strong N–H···O hydrogen-bonding interactions (HBIs). Here, the present paper shows that this is consistent with the largely ignored experimental fact that alkylation of the N–H functionality within M/NH bifunctional Noyori-type catalysts leads to detrimental catalytic activity. Finally, the purpose of this work is to demonstrate that decreasing the strength of this HBI, ultimately to the limit of its complete absence, are conditions under which the same alkylation may lead to beneficial catalytic activity.

Synthesis of Co/N-HNTs composites and investigation on its catalytic activity for H{sub 2} generation

Energy Technology Data Exchange (ETDEWEB)

Zhao, Dongcui; Cheng, Zhilin; Nan, Zhaodong, E-mail: zdnan@yzu.edu.cn

2016-11-01

Co/N-HNTs composites were synthesized via a one-pot solvothermal method, where amine functional halloysite nanotubes (N-HNTs) were used as support materials. Effects of sulfosuccinate sodium salt (AOT), an anionic surfactant, on morphology and dispersibility of Co particles anchored at the N-HNTs were studied. The dispersibility of the Co particles was promoted with the increase of the AOT concentration. The as-obtained composite was used as a catalyst to generate H{sub 2} gas by hydrolysis of NaBH{sub 4} solution. The catalytic activity of the composite was significantly enhanced than the pure Co and Co/graphene composite at the same experimental conditions reported by our laboratory, and the catalyst was conveniently separated from the solution by a magnet. The catalytic activity was enhanced when the dispersibility of the Co particles was improved at the surface of the N-HNTs and the Co content contained in the composite was lowed. At the same time, the Co particles anchored at the inner surface of the N-HNTs resulted in higher catalytic activity, where the Co particles may bond with nitrogen atoms. The activation energy for the hydrolysis of NaBH{sub 4} was calculated to be about 15.42 kJ mol{sup −1}. The catalyst can be continuously used for four times with about the same catalytic activity. - Highlights: • Co/N-HNTs composites are synthesized. • The dispersibility and morphology of the Co particles anchored at the N-HNTs are modified by AOT. • The composite shows higher catalytic activity for production H{sub 2} gas.

Tug-of-war between classical and multicenter bonds in H-(Be)n-H species

Science.gov (United States)

Lundell, Katie A.; Boldyrev, Alexander I.

2018-05-01

Quantum chemical calculations were performed for beryllium homocatenated compounds [H-(Be)n-H]. Global minimum structures were found using machine searches (Coalescence Kick method) with density functional theory. Chemical bonding analysis was performed with the Adaptive Natural Density Partitioning method. It was found that H-(Be)2-H and H-(Be)3-H clusters are linear with classical two-center two-electron bonds, while for n > 3, three-dimensional structures are more stable with multicenter bonding. Thus, at n = 4, multicenter bonding wins the tug-of-war vs. the classical bonding.

Enthalpies of ligand substitution for [Mo(η5C5H5)(CO)2(NO)] – The role of π-bonding effects in metal–ligand bond strengths

International Nuclear Information System (INIS)

Majumdar, Subhojit; Captain, Burjor; Cazin, Catherine S.J.; Nolan, Steven P.; Hoff, Carl D.

2014-01-01

Graphical abstract: - Highlights: • Enthalpies of ligand substitution are measured for Mo(C 5 H 5 )(CO) 2 (NO). • Phosphines and N-heterocyclic carbenes are stronger ligands and displace CO. • Backbonding to π ∗ orbitals is an important part of complex stability. • FTIR studies show shifts to lower wavenumbers of ν-CO and ν-NO. • Structural studies show lengthening of the C-O and N-O bonds. - Abstract: Enthalpies of ligand substitution for [Mo(η 5 -C 5 H 5 )(CO) 2 (NO)] producing [Mo(η 5 -C 5 H 5 )Mo(CO)(L)(NO)] have been measured by solution calorimetry at 30 °C in THF for L = P(OMe) 3 2 2 Ph 3 (SIPr = 1,3-bis(2,6-bis(diisopropylphenyl)imidazolinylidene; IPr = 1,3-bis(2,6-bis(diisopropylphenyl)-imidazol-2-ylidene)). The accepting metal fragment [Mo(η 5 -C 5 H 5 )(CO)(NO)] has a vacant site containing strongly π-accepting carbonyl and nitrosyl ligands and this is shown to influence the stability of the product complex. Infrared studies of both ν CO and ν NO show that metal-to-ligand backbonding increases in the order P(OMe) 3 3 5 -C 5 H 5 )(CO)(IPr)(NO)] and [Mo(η 5 -C 5 H 5 )(CO)(SIPr)(NO)] are reported

Theoretical study of the changes in the vibrational characteristics arising from the hydrogen bonding between Vitamin C ( L-ascorbic acid) and H 2O

Science.gov (United States)

Dimitrova, Yordanka

2006-02-01

The vibrational characteristics (vibrational frequencies, infrared intensities and Raman activities) for the hydrogen-bonded system of Vitamin C ( L-ascorbic acid) with five water molecules have been predicted using ab initio SCF/6-31G(d, p) calculations and DFT (BLYP) calculations with 6-31G(d, p) and 6-31++G(d, p) basis sets. The changes in the vibrational characteristics from free monomers to a complex have been calculated. The ab initio and BLYP calculations show that the complexation between Vitamin C and five water molecules leads to large red shifts of the stretching vibrations for the monomer bonds involved in the hydrogen bonding and very strong increase in their IR intensity. The predicted frequency shifts for the stretching vibrations from Vitamin C taking part in the hydrogen bonding are up to -508 cm -1. The magnitude of the wavenumber shifts is indicative of relatively strong OH···H hydrogen-bonded interactions. In the same time the IR intensity and Raman activity of these vibrations increase upon complexation. The IR intensity increases dramatically (up to 12 times) and Raman activity increases up to three times. The ab initio and BLYP calculations show, that the symmetric OH vibrations of water molecules are more sensitive to the complexation. The hydrogen bonding leads to very large red shifts of these vibrations and very strong increase in their IR intensity. The asymmetric OH stretching vibrations of water, free from hydrogen bonding are less sensitive to the complexation than the hydrogen-bonded symmetric O sbnd H stretching vibrations. The increases of the IR intensities for these vibrations are lower and red shifts are negligible.

H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds

Directory of Open Access Journals (Sweden)

Ibon Alkorta

2016-02-01

Full Text Available A search of the Cambridge Structural Database (CSD was carried out for phosphine-water and arsine-water complexes in which water is either the proton donor in hydrogen-bonded complexes, or the electron-pair donor in pnicogen-bonded complexes. The range of experimental P-O distances in the phosphine complexes is consistent with the results of ab initio MP2/aug’-cc-pVTZ calculations carried out on complexes H2XP:OH2, for X = NC, F, Cl, CN, OH, CCH, H, and CH3. Only hydrogen-bonded complexes are found on the H2(CH3P:HOH and H3P:HOH potential surfaces, while only pnicogen-bonded complexes exist on H2(NCP:OH2, H2FP:OH2, H2(CNP:OH2, and H2(OHP:OH2 surfaces. Both hydrogen-bonded and pnicogen-bonded complexes are found on the H2ClP:OH2 and H2(CCHP:OH2 surfaces, with the pnicogen-bonded complexes more stable than the corresponding hydrogen-bonded complexes. The more electronegative substituents prefer to form pnicogen-bonded complexes, while the more electropositive substituents form hydrogen-bonded complexes. The H2XP:OH2 complexes are characterized in terms of their structures, binding energies, charge-transfer energies, and spin-spin coupling constants 2hJ(O-P, 1hJ(H-P, and 1J(O-H across hydrogen bonds, and 1pJ(P-O across pnicogen bonds.

Recent Advances in Ring-Opening Functionalization of Cycloalkanols by C-C σ-Bond Cleavage.

Science.gov (United States)

Wu, Xinxin; Zhu, Chen

2018-06-01

Cycloalkanols prove to be privileged precursors for the synthesis of distally substituted alkyl ketones and polycyclic aromatic hydrocarbons (PAHs) by virtue of cleavage of their cyclic C-C bonds. Direct functionalization of cyclobutanols to build up other chemical bonds (e. g., C-F, C-Cl, C-Br, C-N, C-S, C-Se, C-C, etc.) has been achieved by using the ring-opening strategy. Mechanistically, the C-C cleavage of cyclobutanols can be involved in two pathways: (a) transition-metal catalyzed β-carbon elimination; (b) radical-mediated 'radical clock'-type ring opening. The recent advances of our group for the ring-opening functionalization of tertiary cycloalkanols are described in this account. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

TEMPO functionalized C{sub 60} fullerene deposited on gold surface for catalytic oxidation of selected alcohols

Energy Technology Data Exchange (ETDEWEB)

Piotrowski, Piotr; Pawłowska, Joanna [University of Warsaw, Department of Chemistry (Poland); Sadło, Jarosław Grzegorz [Institute of Nuclear Chemistry and Technology (Poland); Bilewicz, Renata; Kaim, Andrzej, E-mail: akaim@chem.uw.edu.pl [University of Warsaw, Department of Chemistry (Poland)

2017-05-15

C{sub 60}TEMPO{sub 10} catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C{sub 60}TEMPO{sub 10}@Au composite catalyst had a particle size of 0.5–0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79–98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O{sub 2}/Fe{sup 3+} system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.

Evaluation of Cu as an interlayer in Be/F82H diffusion bonds for ITER TBM

Energy Technology Data Exchange (ETDEWEB)

Hunt, R.M., E-mail: rhunt@ucla.edu [Mechanical and Aerospace Engineering Department, UCLA, 44-128 Engineering IV, 420 Westwood Plaza, Los Angeles, CA 90025-1597 (United States); Goods, S.H., E-mail: shgoods@sandia.gov [Sandia National Laboratories, 7011 East Ave., Livermore, CA 94550 (United States); Ying, A., E-mail: ying@fusion.ucla.edu [Mechanical and Aerospace Engineering Department, UCLA, 44-128 Engineering IV, 420 Westwood Plaza, Los Angeles, CA 90025-1597 (United States); Dorn, C.K., E-mail: christopher_dorn@brushwellman.com [Brush Wellman Inc., 14710 W. Portage River So. Road, Elmore, OH 43416 (United States); Abdou, M., E-mail: abdou@fusion.ucla.edu [Mechanical and Aerospace Engineering Department, UCLA, 44-128 Engineering IV, 420 Westwood Plaza, Los Angeles, CA 90025-1597 (United States)

2011-10-01

Copper has been investigated as a potential interlayer material for diffusion bonds between beryllium and Reduced Activation Ferritic/Martensitic (RAFM) steel. Utilizing Hot Isostatic Pressing (HIP), copper was directly bonded to a RAFM steel, F82H, at 650 deg. C, 700 deg. C, 750 deg. C, 800 deg. C and 850 deg. C, under 103 MPa for 2 h. Interdiffusion across the bonded interface was limited to 1 {mu}m or less, even at the highest HIP'ing temperature. Through mechanical testing it was found that samples HIP'ed at 750 deg. C and above remain bonded up to 211 MPa under tensile loading, at which point ductile failure occurred in the bulk copper. As titanium will be used as a barrier layer to prevent the formation of brittle Be/Cu intermetallics, additional annealing studies were performed on copper samples coated with a titanium thin film to study Ti/Cu interdiffusion characteristics. Samples were heated to temperatures between 650 deg. C and 850 deg. C for 2 h in order to mimic the range of likely HIP temperatures. A correlation was drawn between HIP temperature and diffusion depth for use in determining the minimum Ti film thickness necessary to block diffusion in the Be/F82H joint.

Human acid β-glucosidase: isolation and amino acid sequence of a peptide containing the catalytic site

International Nuclear Information System (INIS)

Dinur, T.; Osiecki, K.M.; Legler, G.; Gatt, S.; Desnick, R.J.; Grabowski, G.A.

1986-01-01

Human acid β-glucosidase (D-glucosyl-N-acylsphingosine glucohydrolase, EC 3.2.1.45) cleaves the glucosidic bonds of glucosylceramide and synthetic β-glucosides. The deficient activity of this hydrolase is the enzymatic defect in the subtypes and variants of Gaucher disease, the most prevalent lysosomal storage disease. To isolate and characterize the catalytic site of the normal enzyme, brominated 3 H-labeled conduritol B epoxide ( 3 H-Br-CBE), which inhibits the enzyme by binding covalently to this site, was used as an affinity label. Under optimal conditions 1 mol of 3 H-Br-CBE bound to 1 mol of pure enzyme protein, indicating the presence of a single catalytic site per enzyme subunit. After V 8 protease digestion of the 3 H-Br-CBE-labeled homogeneous enzyme, three radiolabeled peptides, designated peptide A, B, or C, were resolved by reverse-phase HPLC. The partial amino acid sequence (37 residues) of peptide A (M/sub r/, 5000) was determined. The sequence of this peptide, which contained the catalytic site, had exact homology to the sequence near the carboxyl terminus of the protein, as predicted from the nucleotide sequence of the full-length cDNA encoding acid β-glucosidase

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

Synthesis, structure, and catalytic performance in cyclooctene epoxidation of a molybdenum oxide/bipyridine hybrid material: {[MoO3(bipy)][MoO3(H2O)]}n.

Science.gov (United States)

Abrantes, Marta; Amarante, Tatiana R; Antunes, Margarida M; Gago, Sandra; Paz, Filipe A Almeida; Margiolaki, Irene; Rodrigues, Alírio E; Pillinger, Martyn; Valente, Anabela A; Gonçalves, Isabel S

2010-08-02

The reaction of [MoO(2)Cl(2)(bipy)] (1) (bipy = 2,2'-bipyridine) with water in a Teflon-lined stainless steel autoclave (100 degrees C, 19 h), in an open reflux system with oil bath heating (12 h) or in a microwave synthesis system (120 degrees C, 4 h), gave the molybdenum oxide/bipyridine hybrid material {[MoO(3)(bipy)][MoO(3)(H(2)O)]}(n) (2) as a microcrystalline powder in yields of 72-92%. The crystal structure of 2 determined from synchrotron X-ray powder diffraction data is composed of two distinct neutral one-dimensional polymers: an organic-inorganic polymer, [MoO(3)(bipy)](n), and a purely inorganic chain, [MoO(3)(H(2)O)](n), which are interconnected by O-H...O hydrogen bonding interactions. Compound 2 is a moderately active, stable, and selective catalyst for the epoxidation of cis-cyclooctene at 55 degrees C with tert-butylhydroperoxide (tBuOOH, 5.5 M in decane or 70% aqueous) as the oxidant. Biphasic solid-liquid or triphasic solid-organic-aqueous mixtures are formed, and 1,2-epoxycyclooctane is the only reaction product. When n-hexane is employed as a cosolvent and tBuOOH(decane) is the oxidant, the catalytic reaction is heterogeneous in nature, and the solid catalyst can be recycled and reused without a loss of activity. For comparison, the catalytic performance of the precursor 1 was also investigated. The IR spectra of solids recovered after catalysis indicate that 1 transforms into the organic-inorganic polymer [MoO(3)(bipy)] when the oxidant is tBuOOH(decane) and compound 2 when the oxidant is 70% aqueous tBuOOH.

Catalytical conversion from ortho-H2 to para-H2

International Nuclear Information System (INIS)

Corat, E.J.

1984-01-01

The classical theory of ortho to para-H 2 conversion is discussed, considering the catalytical action of an inhomogeneous magnetic field on a surface with magnetic particles. In particular, the use of charcoal as a catalyst at low temperatures (77 0 K) is considered and some results are presented. The development of a sensor for the determination of para-H 2 concentration in H 2 gas is studied. Experimental results with this sensor are also shown. (Author) [pt

The dimers of glyoxal and acrolein with H 2O and HF: Negative intramolecular coupling and blue-shifted C-H stretch

Science.gov (United States)

Karpfen, Alfred; Kryachko, Eugene S.

2010-04-01

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.

Thermal stability of nanocomposite CrC/a-C:H thin films

International Nuclear Information System (INIS)

Gassner, G.; Mayrhofer, P.H.; Patscheider, J.; Mitterer, C.

2007-01-01

The thermal stability of low-friction Me-C/a-C:H coatings is important for their potential applications in the tool and automotive industry. Recently we showed that CrC x /a-C:H coatings prepared by unbalanced magnetron sputtering of a Cr target in Ar + CH 4 glow discharges exhibit a nanocomposite structure where metastable fcc CrC nanocrystals are encapsulated by an a-C:H phase. Here, we present the structural evolution of these nanocomposite CrC/a-C:H coatings during annealing. High-temperature X-ray diffraction in vacuum and differential scanning calorimetry (DSC) combined with thermo-gravimetric analysis in Ar atmosphere indicate decomposition of the formed metastable fcc CrC phase and subsequent formation of Cr 3 C 2 and Cr 7 C 3 and structural transformation of the a-C:H matrix phase towards higher sp 2 bonding contents at temperatures above 450 deg. C. Combined DSC and mass spectrometer analysis as well as elemental profiling after annealing in vacuum by elastic recoil detection analysis relate this transformation to the loss of bonded hydrogen at temperatures above 200 deg. C. Due to these structural changes the coefficient of friction depends on the annealing temperature of the nanocomposite a-C:H coatings and shows a minimum of ∼ 0.13 for T = 200 deg. C. The more complex tribochemical reactions, influenced by the hydrogen loss from the coating during in-situ high temperatures ball-on disc tests, result in coefficient of friction values below 0.05 for T < 120 deg. C

Role of the H bond network in the radiation chemistry of hydrated systems

International Nuclear Information System (INIS)

Pommeret, S.; Renault, J.P.; Le Caer, S.; Vigneron, G.; Palmer, J.; Lima, M.; Righini, R.

2006-01-01

. Under our conditions, 24 seconds are required to record a spectrum. It is thus possible to follow the evolution of the spectra after irradiation by recording spectra every 30 seconds or every minute for example. The reference is always the non-irradiated sample. FT-IR spectra are obtained from mesoporous silica (MCM-41, a few percent) dispersed in potassium bromide (KBr) pellets. MCM-41 is obtained by a sol-gel process. It is an ordered mesoporous silica with a hexagonal array of one-dimensional pores and a narrow pore-size distribution of about 4 nm. MCM-41 was synthesized in our laboratory as described previously. The glass was baked at 140 degree C for one hour and then at 400 degree C for another hour to remove any carbon contaminates. The glass was then stored overnight at 60 degree C. First results of in situ FT-IR spectra of dried MCM-41 will be presented in the 3000-4000 cm -1 region. Water dynamics at the alumina-air interface: The present communication deals with the dynamical behaviour of OH vibrators at alumina-air interfaces. The OH coverage of alumina is of great importance, as it is known that the adsorption and catalytic properties of γ-alumina are directly associated with the state of its hydroxyl coverage and the nature of the active sites on its surface. Ultrafast infrared-infrared (IR-IR) pump-probe spectroscopy is a powerful tool to investigate the structure and the dynamics of O-H vibrators at interfaces. Previous studies of adsorbed D 2 O on γ-alumina surfaces have been performed using picosecond pump-probe spectroscopy. The new results presented here are using femtosecond pump-probe spectroscopy of OH vibrators on γ-alumina surfaces. The experimental results obtained in this work demonstrate the existence of two kinds of O-H vibrators on the surface of alumina membranes, by distinguishing them by their behaviour on the femtosecond time scale. The first one, whose spectral signature is located in the high frequency region (>3400cm -1

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.

stream_size 26907 stream_content_type text/plain stream_name ChemCatChem_8_1046a.pdf.txt stream_source_info ChemCatChem_8_1046a.pdf.txt Content-Encoding UTF-8 Content-Type text/plain; charset=UTF-8 Author version...: ChemCatChem, vol.8(6); 2016; 1046-1050 Ruthenium(II) catalysed synthesis of pyrrole and indole fused isocoumarins via C-H bond activation in DMF and water† Keisham S. Singh*,a Sneha G. Sawanta, Pierre H. Dixneuf*,b Abstract: Pyrrole and indole...

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

Science.gov (United States)

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

2013-09-02

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.

A theoretical study of the hydrogen bonding between the vic-, cis- and trans-C 2H 2F 2 isomers and hydrogen fluoride

Science.gov (United States)

Rusu, Victor H.; da Silva, João Bosco P.; Ramos, Mozart N.

2009-04-01

MP2/6-31++G(d,p) and B3LYP/6-31++G(d,p) theoretical calculations have been employed to investigate the hydrogen bonding formation involving the vic-, cis- and trans-C 2H 2F 2 isomers and hydrogen fluoride. Our calculations have revealed for each isomer the preferential existence of two possible hydrogen-bonded complexes: a non-cyclic complex and a cyclic complex. For all the three isomers the binding energies for the non-cyclic and cyclic hydrogen complexes are essentially equal using both the MP2 and B3LYP calculations, being that the cyclic structure is slightly more stable. For instance, the binding energies including BSSE and ZPE corrections for the non-cyclic and cyclic structures of cis-C 2H 2F···HF are 8.7 and 9.0 kJ mol -1, respectively, using B3LYP calculations. The cyclic complex formation reduces the polarity, in contrast to what occurs with the non-cyclic complex. This result is more accentuated in vic-C 2H 2F 2···HF. In this latter, Δ μ(cyclic) is -3.07 D, whereas Δ μ(non-cyclic) is +1.92 D using B3LYP calculations. Their corresponding MP2 values are +0.44 D and -1.89 D, respectively. As expected, the complexation produces an H sbnd F stretching frequency downward shift, whereas its IR intensity is enhanced. On the other hand, the vibrational modes of the vic-, cis- and trans-C 2H 2F 2 isomers are little affected by complexation. The new vibrational modes due to hydrogen bonding formation show several interesting features, in particular the HF bending modes which are pure rotations in the free molecule.

A computational mechanistic study of Pd(ii)-catalyzed γ-C(sp3)-H olefination/cyclization of amines: the roles of bicarbonate and ligand effect.

Science.gov (United States)

Liu, Jian-Biao; Tian, Ying-Ying; Zhang, Xin; Wang, Lu-Lin; Chen, De-Zhan

2018-04-03

The detailed mechanism of palladium-catalyzed γ-C(sp3)-H olefination/cyclization of triflyl-protected amines was investigated by density functional theory (DFT) calculations. The olefinated intermediate was initially formed in the first catalytic cycle involving ligand exchange, bicarbonate-assisted C(sp3)-H bond cleavage, alkene insertion and 'reductive β-hydride elimination'. The following syn-addition and reductive elimination furnish the aza-Wacker product. The first step of reductive elimination is the rate-determining step. The mechanism unveils the important roles of bicarbonate: aiding the C-H activation and abstracting the β-proton in the second step of reductive elimination. The parallel bridging mode in the metal-olefin intermediate facilitates the syn-addition, explaining the experimentally observed stereoselectivity. The effect of the monodentate pyridine-based ligands is also discussed.

Z-H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H2 Evolution.

Science.gov (United States)

Belkova, Natalia V; Filippov, Oleg A; Shubina, Elena S

2018-02-01

The ability of neutral transition-metal hydrides to serve as a source of hydride ion H - or proton H + is well appreciated. The hydride ligands possessing a partly negative charge are proton accepting sites, forming a dihydrogen bond, M-H δ- ⋅⋅⋅ δ+ HX (M=transition metal or metalloid). On the other hand, some metal hydrides are able to serve as a proton source and give hydrogen bond of M-H δ+ ⋅⋅⋅X type (X=organic base). In this paper we analyse recent works on transition-metal and boron hydrides showing i) how formation of an intermolecular complex between the reactants changes the Z-H (M-H and X-H) bond polarity and ii) what is the implication of such activation in the mechanisms of hydrides reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triosmium cluster compounds containing isocyanide and hydride ligands. Crystal and molecular structure of (μ-H)(μ-eta1-C==N(H)(t-C4H9))Os3(CO)10

International Nuclear Information System (INIS)

Adams, R.D.; Golembeski, N.M.

1979-01-01

The crystal and molecular structure of the compound (μ-H)(μ-eta 1 -C==N(H)(t-C 4 H 9 ))Os 3 (CO) 10 has been determined by X-ray crystallographic methods. The compound crystallizes in the centrosymmetric monoclinic space group P2 1 /n[C/sub 2h/ 5 ]:a = 13.651 (4) A, b = 9.156 (4) A, c = 18.275 (5) A, β = 111.42 (2) 0 , V = 2126.3 (25) A 3 , Z = 4, rho/sub calcd/ = 2.92 g cm -3 . A uniform triangular cluster of three osmium atoms contains ten linear carbonyl groups and a μ-eta 1 -C==N(H)(t-C 4 H 9 ) iminyl ligand. The carbon atom of the iminyl ligand symmetrically bridges one osmium-osmium bond, as is shown by the internuclear separations Os(2)-C(11) = 2.066 (8) A and Os(3)-C(11) = 2.043 (8) A. The iminyl bond, C(11)-N, is double with the C-N distance being 1.298 (10) A

Rhodium catalyzed regioselective arene homologation of aryl urea via double C-H bond activation and migratory insertion of alkyne

Institute of Scientific and Technical Information of China (English)

Yan Wang; Hao Zhou; Ke Xu; Mei-Hua Shen; Hua-Dong Xu

2017-01-01

A convenient rhodium catalyzed oxidative arene homologation of aniline derivatives with symmetrical or unsymmetrical alkynes using Cu(OAc)2 as oxidant is described.Urea group is shown to be effective as a directing group for initial ortho C-H activation.Two migratory insertion events of alkyne into Rh-C bond occur successively,both with complete regioselectivity.This method is particularly useful for synthesis of polyarenes with different substituents,which has not been reported with conventional protocol.A mechanism has been proposed to explain the observed data.

Rh(I) -Catalyzed Intramolecular Carbonylative C-H/C-I Coupling of 2-Iodobiphenyls Using Furfural as a Carbonyl Source.

Science.gov (United States)

Furusawa, Takuma; Morimoto, Tsumoru; Nishiyama, Yasuhiro; Tanimoto, Hiroki; Kakiuchi, Kiyomi

2016-08-19

Synthesis of fluoren-9-ones by a Rh-catalyzed intramolecular C-H/C-I carbonylative coupling of 2-iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate-determining step is not a C-H bond cleavage but, rather, the oxidative addition of the C-I bond to a Rh(I) center. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Se–H bond of benzeneselenols (ArSe-H): Relationship between bond dissociation enthalpy and spin density of radicals

International Nuclear Information System (INIS)

Nam, Pham Cam; Nguyen, Minh Tho

2013-01-01

Highlights: ► BDE(Se–H)s of C 6 H 5 SeH and its para and meta-substituted derivatives are calculated. ► A relationship between the BDE(Se–H)s and Mulliken atomic spin densities of YC 6 H 4 Se radical is found. ► Good correlations are also observed between the BDE(Se–H)s and the Hammett’s parameters. ► The proton affinity of C 6 H 5 SeH is evaluated to be in the range of 814–818 kJ/mol. ► Ionization energies (IE) of the substituted benzeneselenols are also evaluated. - Abstract: Bond dissociation enthalpies (BDE) of benzeneselenol (ArSe-H) and its para and meta-substituted derivatives are calculated using the (RO)B3LYP/6-311++G(2df,2p)//(U)B3LYP/6-311G(d,p) procedure. The computed BDE(Se–H) = 308 ± 8 kJ/mol for the parent PhSe-H is significantly smaller than the experimental value of 326.4 ± 16.7 kJ/mol [Kenttamaa and coworkers, J. Phys. Chem. 100 (1996) 6608] but larger than a previous value of 280.3 kJ/mol [Newcomb et al., J. Am. Chem. Soc. 113 (1991) 949]. The substituent effects on BDE’s are analyzed in terms of a relationship between BDE(Se–H) and Mulliken atomic spin densities at the Se radical centers of ArSe (π radicals). Good correlations between Hammett’s substituent constants with BDE(Se–H) are established. Proton affinity and ionization energy amount to PA(C 6 H 5 SeH) = 814 ± 4 kJ/mol and IE(C 6 H 5 SeH) = 8.0 ± 0.1 eV. IEs of the substituted benzeneselenols are also determined. Calculated results thus suggest that 4-amino-benzeneselenol derivatives emerge as efficient antioxidants

Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation.

Science.gov (United States)

Pappas, Iraklis; Chirik, Paul J

2016-10-03

The hydrogenolysis of titanium-nitrogen bonds in a series of bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (η 5 -C 5 Me 5 )(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl, [Rh]-H) and (η 5 -C 5 R 5 )(CO) 3 Cr-H ([Cr] R -H, R= H, Me) were evaluated for formal H atom transfer reactivity and were selected due to their relatively weak M-H bond strengths yet ability to activate and cleave molecular hydrogen. Despite comparable M-H BDFEs, disparate reactivity between the two compounds was observed and was traced to the vastly different acidities of the M-H bonds and overall redox potentials of the molecules. With [Rh]-H, catalytic syntheses of ammonia, silylamine and N,N-dimethylhydrazine have been accomplished from the corresponding titanium(IV) complex using H 2 as the stoichiometric H atom source. The data presented in this study provides the thermochemical foundation for the synthesis of NH 3 by proton coupled electron transfer at a well-defined transition metal center.

Cu-catalyzed esterification reaction via aerobic oxygenation and C-C bond cleavage: an approach to α-ketoesters.

Science.gov (United States)

Zhang, Chun; Feng, Peng; Jiao, Ning

2013-10-09

The Cu-catalyzed novel aerobic oxidative esterification reaction of 1,3-diones for the synthesis of α-ketoesters has been developed. This method combines C-C σ-bond cleavage, dioxygen activation and oxidative C-H bond functionalization, as well as provides a practical, neutral, and mild synthetic approach to α-ketoesters which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. A plausible radical process is proposed on the basis of mechanistic studies.

The synthesis of Org 3770 labelled with 3H, 13C and 14C

International Nuclear Information System (INIS)

Kaspersen, F.M.; Rooij, F.A.M. van; Sperling, E.G.M.; Wieringa, J.H.

1989-01-01

The syntheses of 1,2,3,4,10,14b-hexahydro-2-methylpyrazino[2,1-a]pyrido[2,3-c][2]benazepine (Org 3770) labelled with 3 H (and 2 H), 13 C and 14 C are described. Tritiated Org 3770 was prepared either by exchange under alkaline conditions with tritiated water or catalytic reductive dehalogenation of a chloro analogue with 3 H 2 . 13 C-labelled material was obtained in a seven-step synthesis starting from 13 C-labelled benzene whereas 14 C-Org 3770 was prepared in a three-step synthesis starting with 14 CO 2 . All labelled compounds were analyzed by TLC, HPLC, MS and NMR. (author)

Measurements of H-atom density by a catalytic probe

International Nuclear Information System (INIS)

Vesel, A.; Drenik, A.; Mozetic, M.

2006-01-01

One of the important plasma parameters in tokamaks is the density of neutral hydrogen atoms which can be measured by catalytic probes. The method is based on the catalytic recombination of H atoms on the metal surface. In order to prevent a substantial drain of atoms by the probe, it should be made as small as possible. But still this effect can not be neglected. Therefore a study of the influence of a catalytic probe on the H-atom density was performed. The source of neutral H-atoms was inductively coupled RF hydrogen plasma. The gas from the discharge vessel was leaked to an experimental chamber through a narrow tube with the diameter of 5 mm and the length of 6 cm. Charged particles created in the discharge vessel were recombined on the walls of the narrow tube, so that the gas entering the experimental chamber was a mixture of hydrogen atoms and molecules only. The density of H-atoms in the experimental chamber was measured with two nickel catalytic probes. One probe was at fixed position and the other one was made movable. A change in the probe signal of the fixed probe was measured versus the position of the movable probe. The measurements were performed at the pressures between 10 Pa and 200 Pa and at two different RF powers 200 W and 300 W. It was found that the density of neutral hydrogen atoms was reduced for about 20% due to the presence of the probe. This result was independent from the pressure in the experimental chamber. (author)

The Born-Oppenheimer molecular simulations of infrared spectra of crystalline poly-(R)-3-hydroxybutyrate with analysis of weak Csbnd H⋯Odbnd C hydrogen bonds

Science.gov (United States)

Brela, Mateusz Z.; Boczar, Marek; Wójcik, Marek J.; Sato, Harumi; Nakajima, Takahito; Ozaki, Yukihiro

2017-06-01

In this letter we present results of study of weak Csbnd H⋯Odbnd C hydrogen bonds of crystalline poly-(R)-3-hydroxybutyrate (PHB) by using Born-Oppenheimer molecular dynamics. The polymeric structure and IR spectra of PHB result from the presence of the weak hydrogen bonds. We applied the post-molecular dynamics analysis to consider a Cdbnd O motion as indirectly involved in the hydrogen bonds. Quantization of the nuclear motion of the oxygens was done to perform detailed analysis of the strength and properties of the Cdbnd O bands involved in the weak hydrogen bonds. We have also shown the dynamic character of the weak hydrogen bond interactions.

A conserved residue of l-alanine dehydrogenase from Bacillus pseudofirmus, Lys-73, participates in the catalytic reaction through hydrogen bonding.

Science.gov (United States)

He, Guangzheng; Xu, Shujing; Wang, Shanshan; Zhang, Qing; Liu, Dong; Chen, Yuling; Ju, Jiansong; Zhao, Baohua

2018-03-01

A multiple protein sequence alignment of l-alanine dehydrogenases from different bacterial species revealed that five highly conserved amino acid residues Arg-15, Lys-73, Lys-75, His-96 and Asp-269 are potential catalytic residues of l-alanine dehydrogenase from Bacillus pseudofirmus OF4. In this study, recombinant OF4Ald and its mutants of five conserved residues were constructed, expressed in Escherichia coli, purified by His 6 -tag affinity column and gel filtration chromatography, structure homology modeling, and characterized. The purified protein OF4Ald displayed high specificity to l-alanine (15Umg -1 ) with an optimal temperature and pH of 40°C and 10.5, respectively. Enzymatic assay and activity staining in native gels showed that mutations at four conserved residue Arg-15, Lys-75, His-96 and Asp-269 (except residue Lys-73) resulted in a complete loss in enzymatic activity, which signified that these predicted active sites are indispensable for OF4Ald activity. In contrast, the mutant K73A resulted in 6-fold improvement in k cat /K m towards l-alanine as compared to the wild type protein. Further research of the residue Lys-73 substituted by various amino acids and structural modeling revealed that residue Lys-73 might be involved in the catalytic reaction of the enzyme by influencing the enzyme-substrate binding through the hydrogen-bonding interaction with conserved residue Lys-75. Copyright © 2017 Elsevier Inc. All rights reserved.

The isolation of [Pd{OC(O)H}(H)(NHC)(PR3)] (NHC = N-heterocyclic carbene) and its role in alkene and alkyne reductions using formic acid

KAUST Repository

Broggi, Julie; Jurčí k, Vá clav; Songis, Olivier; Poater, Albert; Cavallo, Luigi; Slawin, Alexandra M. Z.; Cazin, Catherine S J

2013-01-01

The [Pd(SIPr)(PCy3)] complex efficiently promotes a tandem process involving dehydrogenation of formic acid and hydrogenation of C-C multiple bonds using H2 formed in situ. The isolation of a key catalytic hydridoformatopalladium species, [Pd{OC(O)H}(H)(IPr)(PCy 3)], is reported. The complex plays a key role in the Pd(0)-mediated formation of hydrogen from formic acid. Mechanistic and computational studies delineate the operational role of the palladium complex in this efficient tandem sequence. © 2013 American Chemical Society.

The isolation of [Pd{OC(O)H}(H)(NHC)(PR3)] (NHC = N-heterocyclic carbene) and its role in alkene and alkyne reductions using formic acid

KAUST Repository

Broggi, Julie

2013-03-27

The [Pd(SIPr)(PCy3)] complex efficiently promotes a tandem process involving dehydrogenation of formic acid and hydrogenation of C-C multiple bonds using H2 formed in situ. The isolation of a key catalytic hydridoformatopalladium species, [Pd{OC(O)H}(H)(IPr)(PCy 3)], is reported. The complex plays a key role in the Pd(0)-mediated formation of hydrogen from formic acid. Mechanistic and computational studies delineate the operational role of the palladium complex in this efficient tandem sequence. © 2013 American Chemical Society.

Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

KAUST Repository

Bukola, Saheed; Merzougui, Belabbes A.; Akinpelu, Akeem; Laoui, Tahar; Hedhili, Mohamed N.; Swain, Greg M.; Shao, Minhua

2014-01-01

Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

KAUST Repository

Bukola, Saheed

2014-11-01

Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts\\' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

Use of the Wilkinson catalyst for the ortho-C-H heteroarylation of aromatic amines: facile access to highly extended π-conjugated heteroacenes for organic semiconductors.

Science.gov (United States)

Huang, Yumin; Wu, Di; Huang, Jingsheng; Guo, Qiang; Li, Juan; You, Jingsong

2014-11-03

An unprecedented catalytic system composed of the Wilkinson catalyst [Rh(PPh3)3Cl] and CF3COOH enabled the highly regioselective cross-coupling of aromatic amines with a variety of heteroarenes through dual C-H bond cleavage. This protocol provided a facile and rapid route from readily available substrates to (2-aminophenyl)heteroaryl compounds, which may be conveniently transformed into highly extended π-conjugated heteroacenes. The experimental studies and calculations showed that thianaphtheno[3,2-b]indoles have large HOMO-LUMO energy gaps and low-lying HOMO levels, and could therefore potentially be high-performance organic semiconductors. Herein we report the first use of a rhodium(I) catalyst for oxidative C-H/C-H coupling reactions. The current innovative catalyst system is much less expensive than [RhCp*Cl2]2/AgSbF6 and could open the door for the application of this approach to other types of C-H activation processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Infrared matrix isolation study of hydrogen bonds involving C-H bonds: Substituent effects

International Nuclear Information System (INIS)

Jeng, M.L.H.; Ault, B.S.

1989-01-01

The matrix isolation technique combined with infrared spectroscopy has been employed to isolate and characterize hydrogen-bonded complexes between a series of substituted alkynes and several oxygen and nitrogen bases. Distinct evidence for hydrogen bond formation was observed in each case, with a characteristic red shift of the hydrogen stretching motion ν r . Shifts between 100 and 300 cm -1 were observed, the largest being for the complex of CF 3 CCH with (CH 3 ) 3 N. The perturbed carbon-carbon triple bond stretching vibration was observed for most complexes, as was the alkynic hydrogen bending motion. Attempts were made to correlate the magnitude of the red shift of ν s with substituent constants for the different substituted alkynes; a roughly linear correlation was found with the Hammett σ parameter. Lack of correlation Δν s with either σ 1 or σ R alone suggests that both inductive and resonance contributions to the strength of the hydrogen-bonding interaction are important

Carbon dioxide utilization via carbonate-promoted C-H carboxylation.

Science.gov (United States)

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

2016-03-10

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.

A bioinspired catalytic aerobic oxidative C-H functionalization of primary aliphatic amines: synthesis of 1,2-disubstituted benzimidazoles.

Science.gov (United States)

Nguyen, Khac Minh Huy; Largeron, Martine

2015-09-01

Aerobic oxidative CH functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of Creative Commons Attribution NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

A PEG/copper(i) halide cluster as an eco-friendly catalytic system for C-N bond formation.

Science.gov (United States)

Li, Cheng-An; Ji, Wei; Qu, Jian; Jing, Su; Gao, Fei; Zhu, Dun-Ru

2018-05-22

The catalytic activities of eight copper(i) halide clusters assembled from copper(i) halide and ferrocenyltelluroethers, 1-8, were investigated in C-N formation under various conditions. A catalytic procedure using poly(ethylene glycol) (PEG-400) as a greener alternative organic solvent has been developed. The PEG-400/5 system can achieve 99% targeted yield with a mild reaction temperature and short reaction time. After the isolation of the products by extraction with diethyl ether, this PEG-400/cluster system could be easily recycled. Spectroscopic studies elucidate a stepwise mechanism: firstly, proton-coupled electron transfer (PCET) involving the transfer of an electron from Cu+ and a proton from imidazole results in the formation of a labile penta-coordinated Cu2+ and aryl radical; the following effective electron transfer from the ferrocene unit reduces Cu2+ and forms the target product; finally, the ferrocenium unit is reduced by the I- anion. The merits of this eco-friendly synthesis are the efficient utilization of reagents and easy recyclability.

Comparative study on catalytic behavior of polynuclear Mg-Mo-complex and FeMo-co-factor of nitrogenase in reactions with C2H2, N2 and CO

International Nuclear Information System (INIS)

Bardina, N.V.; Bazhenova, T.A.; Petrova, G.N.; Shilova, A.K.; Shilov, A.E.

2006-01-01

Catalytic reduction kinetics of C 2 H 2 in the presence of the Mg-Mo-cluster {[Mg 2 Mo 8 O 22 (MeO) 6 (MeOH) 4 ] 2- [Mg(MeOH) 6 ] 2+ }·6MeOH 1 is studied. Several interdependent coordinating centers are active in reference to substrates and inhibitors in the polynuclear Mg-Mo-complex, as in the reduced by europium amalgam (μ 6 -N)MoFe 7 S 9 ·homocitrate (FeMoco, 2). Comparison of regularities in reduction mechanism of C 2 H 2 , N 2 and CO with the participation of synthetic polynuclear complex 1 and natural cluster 2 is conducted. Regularities of the studied reactions in the systems involving natural catalytic cluster FeMoco and the synthetic Mg-Mo-complex modelling of its effect are noted to be similar. The main variations the systems show as regards to the reaction with molecular nitrogen [ru

Activation and thermodynamic parameter study of the heteronuclear C=O···H-N hydrogen bonding of diphenylurethane isomeric structures by FT-IR spectroscopy using the regularized inversion of an eigenvalue problem.

Science.gov (United States)

Spegazzini, Nicolas; Siesler, Heinz W; Ozaki, Yukihiro

2012-08-02

The doublet of the ν(C=O) carbonyl band in isomeric urethane systems has been extensively discussed in qualitative terms on the basis of FT-IR spectroscopy of the macromolecular structures. Recently, a reaction extent model was proposed as an inverse kinetic problem for the synthesis of diphenylurethane for which hydrogen-bonded and non-hydrogen-bonded C=O functionalities were identified. In this article, the heteronuclear C=O···H-N hydrogen bonding in the isomeric structure of diphenylurethane synthesized from phenylisocyanate and phenol was investigated via FT-IR spectroscopy, using a methodology of regularization for the inverse reaction extent model through an eigenvalue problem. The kinetic and thermodynamic parameters of this system were derived directly from the spectroscopic data. The activation and thermodynamic parameters of the isomeric structures of diphenylurethane linked through a hydrogen bonding equilibrium were studied. The study determined the enthalpy (ΔH = 15.25 kJ/mol), entropy (TΔS = 14.61 kJ/mol), and free energy (ΔG = 0.6 kJ/mol) of heteronuclear C=O···H-N hydrogen bonding by FT-IR spectroscopy through direct calculation from the differences in the kinetic parameters (δΔ(‡)H, -TδΔ(‡)S, and δΔ(‡)G) at equilibrium in the chemical reaction system. The parameters obtained in this study may contribute toward a better understanding of the properties of, and interactions in, supramolecular systems, such as the switching behavior of hydrogen bonding.

Atomistic Frictional Properties of the C(1002x1-H Surface

Directory of Open Access Journals (Sweden)

Paul M. Jones

2013-01-01

Full Text Available Density functional theory- (DFT- based ab initio calculations were used to investigate the surface-to-surface interaction and frictional behavior of two hydrogenated C(100 dimer surfaces. A monolayer of hydrogen atoms was applied to the fully relaxed C(1002x1 surface having rows of C=C dimers with a bond length of 1.39 Å. The obtained C(1002x1-H surfaces (C–H bond length 1.15 Å were placed in a large vacuum space and translated toward each other. A cohesive state at a surface separation of 4.32 Å that is stabilized by approximately 0.42 eV was observed. An increase in the charge separation in the surface dimer was calculated at this separation having a 0.04 e transfer from the hydrogen atom to the carbon atom. The Mayer bond orders were calculated for the C–C and C–H bonds and were found to be 0.962 and 0.947, respectively. σ C–H bonds did not change substantially from the fully separated state. A significant decrease in the electron density difference between the hydrogen atoms on opposite surfaces was seen and assigned to the effects of Pauli repulsion. The surfaces were translated relative to each other in the (100 plane, and the friction force was obtained as a function of slab spacing, which yielded a 0.157 coefficient of friction.

Bifunctional RuII -Complex-Catalysed Tandem C-C Bond Formation: Efficient and Atom Economical Strategy for the Utilisation of Alcohols as Alkylating Agents.

Science.gov (United States)

Roy, Bivas Chandra; Chakrabarti, Kaushik; Shee, Sujan; Paul, Subhadeep; Kundu, Sabuj

2016-12-12

Catalytic activities of a series of functional bipyridine-based Ru II complexes in β-alkylation of secondary alcohols using primary alcohols were investigated. Bifunctional Ru II complex (3 a) bearing 6,6'-dihydroxy-2,2'-bipyridine (6DHBP) ligand exhibited the highest catalytic activity for this reaction. Using significantly lower catalyst loading (0.1 mol %) dehydrogenative carbon-carbon bond formation between numerous aromatic, aliphatic and heteroatom substituted alcohols were achieved with high selectivity. Notably, for the synthesis of β-alkylated secondary alcohols this protocol is a rare one-pot strategy using a metal-ligand cooperative Ru II system. Remarkably, complex 3 a demonstrated the highest reactivity compared to all the reported transition metal complexes in this reaction. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A rod-packing microporous hydrogen-bonded organic framework for highly selective separation of C2H2/CO2at room temperature

KAUST Repository

Li, Peng

2014-11-13

Self-assembly of a trigonal building subunit with diaminotriazines (DAT) functional groups leads to a unique rod-packing 3D microporous hydrogen-bonded organic framework (HOF-3). This material shows permanent porosity and demonstrates highly selective separation of C2H2/CO2 at ambient temperature and pressure.

A rod-packing microporous hydrogen-bonded organic framework for highly selective separation of C2H2/CO2at room temperature

KAUST Repository

Li, Peng; He, Yabing; Zhao, Yunfeng; Weng, Linhong; Wang, Hailong; Krishna, Rajamani A A; Wu, Hui; Zhou, Wei; O'Keeffe, Michael A.; Han, Yu; Chen, Banglin

2014-01-01

Self-assembly of a trigonal building subunit with diaminotriazines (DAT) functional groups leads to a unique rod-packing 3D microporous hydrogen-bonded organic framework (HOF-3). This material shows permanent porosity and demonstrates highly selective separation of C2H2/CO2 at ambient temperature and pressure.

Ligand-controlled, tunable silver-catalyzed C-H amination.

Science.gov (United States)

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

2014-12-03

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.

Corrosion of glass-bonded sodalite as a function of pH and temperature

International Nuclear Information System (INIS)

Morss, L. R.; Stanley, M.; Tatko, C.; Ebert, W. L.

1999-01-01

This paper reports the results of corrosion tests with monoliths of sodalite, binder glass, and glass-bonded sodalite, a ceramic waste form (CWF) that is being developed to immobilize radioactive electrorefiner salt used to condition spent sodium-bonded nuclear fuel. These tests were performed with dilute pH-buffered solutions in the pH range of 5-10 at temperatures of 70 and 90 C. The pH dependence of the forward dissolution rates of the CWF and its components have been determined. The pH dependence of the dissolution rates of sodalite, binder glass, and glass-bonded sodalite are similar to the pH dependence of dissolution rate of borosilicate nuclear waste glasses, with a negative pH dependence in the acidic region and a positive pH dependence in the basic region. Our results on the forward dissolution rates and their temperature and pH dependence will be used as components of a waste form degradation model to predict the long-term behavior of the CWF in a nuclear waste repository

Interconversion of η3-H2SiRR' σ-complexes and 16-electron silylene complexes via reversible H-H or C-H elimination.

Science.gov (United States)

Lipke, Mark C; Neumeyer, Felix; Tilley, T Don

2014-04-23

Solid samples of η(3)-silane complexes [PhBP(Ph)3]RuH(η(3)-H2SiRR') (R,R' = Et2, 1a; PhMe, 1b; Ph2, 1c, MeMes, 1d) decompose when exposed to dynamic vacuum. Gas-phase H2/D2 exchange between isolated, solid samples of 1c-d3 and 1c indicate that a reversible elimination of H2 is the first step in the irreversible decomposition. An efficient solution-phase trap for hydrogen, the 16-electron ruthenium benzyl complex [PhBP(Ph)3]Ru[η(3)-CH2(3,5-Me2C6H3)] (3) reacts quantitatively with H2 in benzene via elimination of mesitylene to form the η(5)-cyclohexadienyl complex [PhBP(Ph)3]Ru(η(5)-C6H7) (4). This H2 trapping reaction was utilized to drive forward and quantify the elimination of H2 from 1b,d in solution, which resulted in the decomposition of 1b,d to form 4 and several organosilicon products that could not be identified. Reaction of {[PhBP(Ph)3]Ru(μ-Cl)}2 (2) with (THF)2Li(SiHMes2) forms a new η(3)-H2Si species [PhBP(Ph)3]Ru[CH2(2-(η(3)-H2SiMes)-3,5-Me2C6H2)] (5) which reacts with H2 to form the η(3)-H2SiMes2 complex [PhBP(Ph)3]RuH(η(3)-H2SiMes2) (1e). Complex 1e was identified by NMR spectroscopy prior to its decomposition by elimination of Mes2SiH2 to form 4. DFT calculations indicate that an isomer of 5, the 16-electron silylene complex [PhBP(Ph)3]Ru(μ-H)(═SiMes2), is only 2 kcal/mol higher in energy than 5. Treatment of 5 with XylNC (Xyl = 2,6-dimethylphenyl) resulted in trapping of [PhBP(Ph)3]Ru(μ-H)(═SiMes2) to form the 18-electron silylene complex [PhBP(Ph)3]Ru(CNXyl)(μ-H)(═SiMes2) (6). A closely related germylene complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)](H)(═GeH(t)Bu) (8) was prepared from reaction of (t)BuGeH3 with the benzyl complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)][η(1)-CH2(3,5-Me2C6H3)] (7). Single crystal XRD analysis indicated that unlike for 6, the hydride ligand in 8 is a terminal hydride that does not engage in 3c-2e Ru-H → Ge bonding. Complex 1b is an effective precatalyst for the catalytic Ge-H dehydrocoupling

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.

1990-01-01

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

Theoretical characterizations of novel C2H5O+ reactions

Science.gov (United States)

Hudson, Charles E.; McAdoo, David J.

2004-03-01

Assorted reactions of C2H5O+ isomers are characterized by theory, including tracing their courses by means of intrinsic reaction coordinate computations. We establish that CH3CH=OH+ eliminates methane by transferring H from oxygen to a methyl hydrogen and then to the CC bond to produce CHO++CH4. This adds to the limited knowledge of the involvement of hypervalent structures in the reactions of cations in the gas phase. Second, we characterized the course of CH3CH=OH+-->H3O++HC[triple bond; length as m-dash]CH. In this dissociation, H first migrates from the methyl to the oxygen to give O-protonated vinyl alcohol, a stable intermediate. Then the H2O swings outward to over the middle of the CC bond while one of the two hydrogens on the non-O-bearing carbon revolves to between the oxygen and the two carbons, leading to formation of a [H3O+ HC[triple bond; length as m-dash]CH] complex. This complex contains sufficient energy to dissociate its partners because a high barrier is crossed in its formation. Third, we found that methane elimination from CH3O+=CH2 involves stretching of the CH3---O bond and then rotation of the methyl so that a methyl hydrogen is pointed directly toward the oxygen. This reaction is completed by further rotation of the methyl to abstract a methylene hydrogen to the opposite side of the methyl from that initially bonded to oxygen. This clearly establishes that this dissociation takes place through an ion-neutral complex. Each of the reaction coordinates for the three preceding reactions traverses a novel bonding stage involving H, evidence that such are not unusual in gas phase ion chemistry. Finally, we showed that in the rearrangement CH3O+=CH2-->CH2=O+CH3, before Ht is transferred CH2 rotates around the C=C bond from being in the skeletal plane to being perpendicular to it, and Ht remains in the skeletal plane throughout its transfer. This pathway appears to balance avoiding an orbital symmetry-forbidden suprafacial transition state with

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

Science.gov (United States)

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

2015-05-11

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.

13C Kinetic isotopic effect of polymerization on monomers with multiple bond

International Nuclear Information System (INIS)

Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

1988-01-01

13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

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)

2009-05-12

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.

Effect of aromatization of the ring on intramolecular H-bond in 3-hydroxy-4-formylo derivatives of fulvene

Science.gov (United States)

Oziminski, Wojciech P.; Krygowski, Tadeusz M.

2011-06-01

DFT optimization of H-bonded 3-hydroxy-4-formylo derivatives of fulvene aromatized by amino substitution at C6 or by complexation with Li atom was performed using the B3LYP functional together with 6-311+G(d,p) basis set. Several aromaticity indicators (HOMA, NICS, pEDA and Shannon aromaticity) confirm an increase of aromaticity in the sequence: fulvene, 6-aminofulvene, Li-complex with fulvene and in the case of H-bonded 3-hydroxy-4-formylo derivatives, exhibited in the same sequence an increase of H-bond strength estimated by direct comparison of energy for H-bonded and open conformations, as well as by using AIM based electron densities at bond critical point.

X-ray and Hydrogen-bonding Properties of 1-((1H-benzotriazol-1-ylmethylnaphthalen-2-ol

Directory of Open Access Journals (Sweden)

Jaime Ríos-Motta

2009-03-01

Full Text Available The solid state structure of 1-((1H-benzotriazol-1-ylmethylnaphthalen-2-ol, C17H13N3O, shows that this Mannich base crystallizes forming intermolecular N···HO hydrogen bonds, rather than intramolecular ones. Factors contributing to this choice of hydrogen-bonding mode are discussed. The compound crystallizes in the monoclinic system, P21/c space group, with lattice constants: a = 11.7934(9 Å, b = 14.3002(14 Å, c = 8.4444(8 Å, β = 106.243(5 deg, V = 1367.3(2 Å3, Z = 4, F(000 = 576, R1 = 6.96%, wR2 = 11.4%.

Recent Developments in C-H Activation for Materials Science in the Center for Selective C-H Activation.

Science.gov (United States)

Zhang, Junxiang; Kang, Lauren J; Parker, Timothy C; Blakey, Simon B; Luscombe, Christine K; Marder, Seth R

2018-04-16

Abstract : Organic electronics is a rapidly growing field driven in large part by the synthesis of ∏-conjugated molecules and polymers. Traditional aryl cross-coupling reactions such as the Stille and Suzuki have been used extensively in the synthesis of ∏-conjugated molecules and polymers, but the synthesis of intermediates necessary for traditional cross-couplings can include multiple steps with toxic and hazardous reagents. Direct arylation through C-H bond activation has the potential to reduce the number of steps and hazards while being more atom-economical. Within the Center for Selective C-H Functionalization (CCHF), we have been developing C-H activation methodology for the synthesis of ∏-conjugated materials of interest, including direct arylation of difficult-to-functionalize electron acceptor intermediates and living polymerization of ∏-conjugated polymers through C-H activation.

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

Science.gov (United States)

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

2018-01-02

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.

Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

Science.gov (United States)

Yik, Edwin Shyn-Lo

convergence to a single phase is expected and predictable from thermodynamics at a given temperature and sulfur chemical potential, metastability of two phases can exist. We demonstrate, through extensive characterization and kinetic evidence, such behaviors exist in Re, where structural disparities between its phases lead to kinetic hurdles that prevent interconversions between layered ReSx nanostructures and sulfur-covered Re metal clusters. Such features allowed, for the first time, direct comparisons of reaction rates at identical conditions on two disparate phases of the same transition metal identity. Rigorous assessments of kinetic and selectivity data indicated that more universal mechanistic features persist across all catalysts studied, suggesting that differences in their catalytic activity were the result of different densities of HDS sites, which appeared to correlate with their respective metal-sulfur bond energies. Kinetic responses and product distributions indicated that the consumption of thiophene proceeds by the formation of a partially-hydrogenated surface intermediate, which subsequently produces tetrahydrothiophene (THT) and butene/butane (C4) via primary routes on similar types of sites. These sites are formed from desorption of weakly-bound sulfur adatoms on sulfur-covered metal surfaces, which can occur when the heat of sulfur adsorption is sufficiently low at high sulfur coverage as a result of increased sulfur-sulfur repulsive interactions. Relative stabilities and differences in the molecularity of the respective transition states that form THT and C4 dictate product distributions. THT desulfurization to form C4 occurs via readsorption and subsequent dehydrogenation, evidenced by secondary rates that exhibited negative H2 dependences. These behaviors suggest that C-S bond activation occurs on a partially (un)saturated intermediate, analogous to behaviors observed in C-C bond scission reactions of linear and cycloalkanes on hydrogen-covered metal

Comparison of FeS, FeS + S and solid superacid catalytic properties for coal hydro-liquefaction

Energy Technology Data Exchange (ETDEWEB)

Zhicai Wang; Hengfu Shui; Dexiang Zhang; Jinsheng Gao [East China University of Science and Technology, Shanghai (China). College of Resource and Environment Engineering

2007-03-15

Catalyst plays an important role in direct coal liquefaction. This paper focuses on the catalytic behavior of a novel SO{sub 4}{sup 2-}/ZrO{sub 2} superacid catalyst in coal hydro-liquefaction. A series of hydro-liquefaction experiments were conducted under mild conditions - 400{sup o}C, 30 min and H{sub 2} initial pressure 4 MPa in a batch autoclave with a volume of 100 ml. The catalytic property of SO{sub 4}{sup 2-}/ZrO{sub 2} was compared with FeS and FeS + S by Shenhua coal. The liquefaction products catalyzed by different catalysts were analyzed by FTIR spectrum, {sup 1}H NMR spectrum and element analysis. In addition, the SO{sub 4}{sup 2-}/ZrO{sub 2} solid superacid was characterized. The results indicated that the SO{sub 4}{sup 2-}/ZrO{sub 2} solid superacid shows outstanding catalytic property for direct liquefaction of coal and gives the highest coal conversion and gas + oil yield compared to other two catalysts. The THF conversion and the extraction yield of CS{sub 2}/NMP mixed solvent of liquefied coal catalyzed with SO{sub 4}{sup 2-}/ZrO{sub 2} are 76.3%, daf and 81.2%, daf respectively, and the yield of gas + oil is 62.5%, daf under the condition used in this study. The pyrolysis of coal macromolecular clusters can be promoted by catalysts such as FeS, FeS + S and SO{sub 4}{sup 2-}/ZrO{sub 2}. There may be only the pyrolysis of volatile matter and the relaxation of the structure of coal macromolecular clusters in non-catalytic liquefaction at 400{sup o}C. Added sulfur in FeS can improve the catalytic activity of hydrogenation. SO{sub 4}{sup 2-}/ZrO{sub 2} is a notable catalyst in the study of coal direct liquefaction because it shows excellent catalytic activities for the pyrolysis and the hydrogenation. In addition, it has been found that the C-O bond is the most stable group in coal liquefaction reaction except for the covalent bond between carbon and carbon. 34 refs., 6 figs., 6 tabs.

Regioselective C-H imidation of five-membered heterocyclic compounds through a metal catalytic or organocatalytic approach.

Science.gov (United States)

Wang, Xin; Sun, Kai; Lv, Yunhe; Ma, Fengji; Li, Gang; Li, Donghui; Zhu, Zhonghong; Jiang, Yongqing; Zhao, Feng

2014-12-01

An efficient method for the synthesis of 2-amino and β-amino five-membered heterocyclic derivatives that are closely related to a variety of biologically active natural products is described. Regioselectivity was achieved through a metal catalytic or organocatalytic approach. Preliminary studies on the reaction mechanism suggest a radical imidation pathway; however, further studies are needed to verify the mechanism. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of H3-labelled methyl ethers of saturated fatty acids by heterogeneous catalytic isotope exchange in solution with gaseous tritium

International Nuclear Information System (INIS)

Shevchenko, V.P.; Myasoedov, N.F.

1980-01-01

A simple method of preparing 3 H-labelled methyl ethers of saturated fatty acids in the dioxane solution using the method of isotopic heterogenous catalytic exchange with gaseous tritium, is suggested. 3 H-labelled natural fatty acids (C 12 -C 18 ) are prepared by alkaline hydrolysis [ru

Cobalt-Catalyzed C(sp(2))-H Borylation: Mechanistic Insights Inspire Catalyst Design.

Science.gov (United States)

Obligacion, Jennifer V; Semproni, Scott P; Pappas, Iraklis; Chirik, Paul J

2016-08-24

A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.

Performance of vacuum plasma spray and HVOF bond coatings at 900° and 1100 °C

Energy Technology Data Exchange (ETDEWEB)

Lance, Michael J. [ORNL; Haynes, James A. [ORNL; Pint, Bruce A. [ORNL

2017-12-01

The effects of Ti and B additions to a vacuum plasma sprayed (VPS) NiCoCrAlYHfSi bond coating on thermal barrier coating (TBC) performance were studied at 1100 °C and 900 °C and compared to high-velocity oxy-fuel (HVOF) bond coatings. Using alloy 247 substrates and air plasma sprayed Y2O3-stabilized ZrO2 top coatings, additions of B or Ti + B did not improve the average TBC lifetime in 1-h cycles at 1100 °C in air with 10% H2O. The addition of Ti resulted in a decrease in lifetime. Photo-stimulated luminescence spectroscopy was used to map residual stresses in the thermally-grown Al2O3 scale. At 900 °C, closer to a typical land based turbine operating bond coating temperature, specimens were examined after ten 500-h cycles in laboratory air and air with 10%H2O to study the effect of H2O. The addition of water vapor had little effect on the measured parabolic rate constants at 900 °C and a comparison of the oxide microstructures in both environments is reported.

Development of HIP bonding procedure and mechanical properties of HIP bonded joints for reduced activation ferritic steel F-82H

International Nuclear Information System (INIS)

Oda, Masahiro; Kurasawa, Toshimasa; Kuroda, Toshimasa; Hatano, Toshihisa; Takatsu, Hideyuki

1997-03-01

Structural materials of blanket components in fusion DEMO reactors will receive a neutron wall load more than 3-5MW/m 2 as well as exposed by surface heat flux more than 0.5MW/m 2 . A reduced activation ferritic steel F-82H has been developed by JAERI in collaboration with NKK from viewpoints of resistance for high temperature and neutron loads and lower radioactivity. This study intends to obtain basic performance of F-82H to establish the fabrication procedure of the first wall and blanket box by using Hot Isostatic Pressing (HIP) bonding. Before HIP bonding tests, effects of heat treatment temperature and surface roughness on mechanical properties of joints were investigated in the heat treatment tests and diffusion bonding tests, respectively. From these results, the optimum HIP bonding conditions and the post heat treatment were selected. Using these conditions, the HIP bonding tests were carried out to evaluate HIP bondability and to obtain mechanical properties of the joints. Sufficient HIP bonding performance was obtained under the temperature of 1040degC, the compressive stress of 150MPa, the holding time of 2h, and the surface roughness ∼μ m. Mechanical properties of HIP bonded joints with these conditions were similar to those of as-received base metal. An oxide formation on the surface to be bonded would need to be avoided for sufficient bonding. The bonding ratio, Charpy impact value and fatigue performance of the joints strongly depended on the HIP conditions, especially temperature, while micro-structure, Vickers hardness and tensile properties had little dependence on the HIP temperature. The surface roughness strongly affected the bonding ratio and would be required to be in the level of a few μ m. In the HIP bonding test of the welded material, the once-melted surface could be jointed by the HIP bonding under the above-mentioned procedure. (J.P.N.)

Rhodium(I)-catalyzed cycloisomerization of benzylallene-alkynes through C-H activation.

Science.gov (United States)

Kawaguchi, Yasuaki; Yasuda, Shigeo; Kaneko, Akira; Oura, Yuki; Mukai, Chisato

2014-07-14

The efficient Rh(I)-catalyzed cycloisomerization of benzylallene-alkynes produced the tricyclo[9.4.0.0(3,8)]pentadecapentaene skeleton through a C(sp2)-H bond activation in good yields. A plausible reaction mechanism proceeds via oxidative addition of the acetylenic C-H bond to Rh(I), an ene-type cyclization to the vinylidenecarbene-Rh(I) intermediate, and an electrophilic aromatic substitution with the vinylidenecarbene species. It was proposed based on deuteration and competition experiments. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies of Metal-Metal Bonded Compounds in Catalysis

Energy Technology Data Exchange (ETDEWEB)

Berry, John F. [Univ. of Wisconsin, Madison, WI (United States)

2018-01-19

The overall goals of this research are (1) to define the fundamental coordination chemistry underlying successful catalytic transformations promoted by metal-metal bonded compounds, and (2) to explore new chemical transformations that occur at metal-metal bonded sites that could lead to the discovery of new catalytic processes. Transformations of interest include metal-promoted reactions of carbene, nitrene, or nitrido species to yield products with new C–C and C–N bonds, respectively. The most promising suite of transition metal catalysts for these transformations is the set of metal-metal bonded coordination compounds of Ru and Rh of the general formula M₂(ligand)₄, where M = Ru or Rh and ligand = a monoanionic, bridging ligand such as acetate. Development of new catalysts and improvement of catalytic conditions have been stymied by a general lack of knowledge about the nature of highly reactive intermediates in these reactions, the knowledge that is to be supplied by this work. Our three specific objectives for this year have been (A) to trap, isolate, and characterize new reactive intermediates of general relevance to catalysis, (B) to explore the electronic structure and reactivity of these unusual species, and how these two properties are interrelated, and (C) to use our obtained mechanistic knowledge to design new catalysts with a focus on Earth-abundant first-row transition metal compounds.

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

2011-01-01

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...

Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

Science.gov (United States)

Souillart, Laetitia; Cramer, Nicolai

2014-09-01

The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom-economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)-catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Control activity of yeast geranylgeranyl diphosphate synthase from dimer interface through H-bonds and hydrophobic interaction.

Science.gov (United States)

Chang, Chih-Kang; Teng, Kuo-Hsun; Lin, Sheng-Wei; Chang, Tao-Hsin; Liang, Po-Huang

2013-04-23

Previously we showed that yeast geranylgeranyl diphosphate synthase (GGPPS) becomes an inactive monomer when the first N-terminal helix involved in dimerization is deleted. This raises questions regarding why dimerization is required for GGPPS activity and which amino acids in the dimer interface are essential for dimerization-mediated activity. According to the GGPPS crystal structure, three amino acids (N101, N104, and Y105) located in the helix F of one subunit are near the active site of the other subunit. As presented here, when these residues were replaced individually with Ala caused insignificant activity changes, N101A/Y105A and N101A/N104A but not N104A/Y105A showed remarkably decreased k(cat) values (200-250-fold). The triple mutant N101A/N104A/Y105A displayed no detectable activity, although dimer was retained in these mutants. Because N101 and Y105 form H-bonds with H139 and R140 in the other subunit, respectively, we generated H139A/R140A double mutant and found it was inactive and became monomeric. Therefore, the multiple mutations apparently influence the integrity of the catalytic site due to the missing H-bonding network. Moreover, Met111, also on the highly conserved helix F, was necessary for dimer formation and enzyme activity. When Met111 was replaced with Glu, the negative-charged repulsion converted half of the dimer into a monomer. In conclusion, the H-bonds mainly through N101 for maintaining substrate binding stability and the hydrophobic interaction of M111 in dimer interface are essential for activity of yeast GGPPS.

Probing electron density of H-bonding between cation-anion of imidazolium-based ionic liquids with different anions by vibrational spectroscopy.

Science.gov (United States)

Gao, Yan; Zhang, Liqun; Wang, Yong; Li, Haoran

2010-03-04

Attenuated total reflection infrared spectroscopy and density functional theory calculation have been employed to study the spectral properties of imidazolium-based ionic liquids (ILs) with different anions. ILs based on 1-butyl-3-methylimidazolium cation with different anions, OH(-), CF(3)CO(2)(-), HSO(4)(-), H(2)PO(4)(-), Cl(-), PF(6)(-), and BF(4)(-), are investigated in the present work. It has been shown that the C(2)-H stretching vibration of the imidazolium ring is closely related to the electron density of H-bonding between the two closest cations and anions for pure ILs. The electron density of H-bonding between cation and anion with different anions decreases in the order [OH](-) > [H(2)PO(4)](-) > [HSO(4)](-) > [CF(3)CO(2)](-) > [Cl](-) > [BF(4)](-) > [PF(6)](-). For aqueous ILs, with increasing water content, the aromatic C-H stretching vibration of the imidazolium cation showed systematic blue-shifts. Especially for BmimOH, the nu(C(2))(-H) undergoes a drastic blue-shift by 58 cm(-1), suggesting that the formation of the strong hydrogen bonds O-H...O may greatly weaken the electron density of H-bonding between the cation and anion of ILs.

Catalytic Cascade Dehydration-Etherification of Fructose into 5-Ethoxymethylfurfural with SO3H-Functionalized Polymers

Directory of Open Access Journals (Sweden)

Hu Li

2014-01-01

Full Text Available A series of SO3H-functionalized polymers were prepared and employed as heterogeneous catalysts for one-pot transformation of fructose into 5-ethoxymethylfurfural (EMF that is considered to be one of potential liquid biofuels. A high EMF yield of 72.8% could be obtained at 110°C for 10 h, and the polymeric acid catalysts could be recycled for five times without significant loss of catalytic performance.

properties of Cr(C,N) hard coatings deposited in Ar-C2H2-N2 plasma

International Nuclear Information System (INIS)

Macek, M.; Cekada, M.; Kek, D.; Panjan, P.

2002-01-01

Mechanical properties, microstructure and the average chemical composition of Cr(C,N) hard coatings deposited in Ar-C 2 H 2 -N 2 plasma strongly depends on the partial pressure of the reactive gases (N 2 , C 2 H 2 ) and on the type of the deposition equipment. In this study we report on the properties of Cr(C,N) hard coatings deposited by means of the triode ion plating in the BAI 730 apparatus and those prepared by sputter deposition in Balzers Sputron in the pressure range from 0.12 Pa (pure Ar) up to 0.35 Pa with different ratios (0-100%) between C 2 H 2 and N 2 . At first mechanical properties (microhardness and adhesion) of coatings were analyzed on the common way. Internal stress was measured by the radius of substrate curvature. Chemical composition of coatings was analyzed by means of AES while the Raman and XPS spectroscopy was used to determined the nature of carbon bonding in the Cr(C,N) films. Microstructure was determined by XRD as well as by means of TEM and TED. Chemical state of various elements in the coating has been studied by XPS. The ratio of the carbide bond (C-Cr) against the C-C and C-H bonds was calculated. The existence of the graphite phase in some Cr(C,N) coatings was confirmed by Raman spectroscopy. (Authors)

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

13C, 1H spin-spin coupling constants. Pt. 4

International Nuclear Information System (INIS)

Aydin, R.; Guenther, H.

1979-01-01

One-bond, geminal, and vicinal 13 C, 1 H coupling constants have been determined for adamantane using α-and β-[D]adamantane and the relation sup(n)J( 13 C, 1 H)=6,5144sup(n)J( 13 C, 2 H) for the conversion of the measured sup(n)J( 13 C, 2 H) values. It is shown that the magnitude of 3 Jsub(trans) is strongly influenced by the substitution pattern. Relative H,D isotope effects for 13 C chemical shifts are given. (orig.) [de

The role of short-range Cys171-Cys178 disulfide bond in maintaining cutinase active site integrity: A molecular dynamics simulation

International Nuclear Information System (INIS)

Matak, Mehdi Youssefi; Moghaddam, Majid Erfani

2009-01-01

Understanding structural determinants in enzyme active site integrity can provide a good knowledge to design efficient novel catalytic machineries. Fusarium solani pisi cutinase with classic triad Ser-His-Asp is a promising enzyme to scrutinize these structural determinants. We performed two MD simulations: one, with the native structure, and the other with the broken Cys171-Cys178 disulfide bond. This disulfide bond stabilizes a turn in active site on which catalytic Asp175 is located. Functionally important H-bonds and atomic fluctuations in catalytic pocket have been changed. We proposed that this disulfide bond within active site can be considered as an important determinant of cutinase active site structural integrity.

Reaction mechanisms at 4H-SiC/SiO2 interface during wet SiC oxidation

Science.gov (United States)

Akiyama, Toru; Hori, Shinsuke; Nakamura, Kohji; Ito, Tomonori; Kageshima, Hiroyuki; Uematsu, Masashi; Shiraishi, Kenji

2018-04-01

The reaction processes at the interface between SiC with 4H structure (4H-SiC) and SiO2 during wet oxidation are investigated by electronic structure calculations within the density functional theory. Our calculations for 4H-SiC/SiO2 interfaces with various orientations demonstrate characteristic features of the reaction depending on the crystal orientation of SiC: On the Si-face, the H2O molecule is stable in SiO2 and hardly reacts with the SiC substrate, while the O atom of H2O can form Si-O bonds at the C-face interface. Two OH groups are found to be at least necessary for forming new Si-O bonds at the Si-face interface, indicating that the oxidation rate on the Si-face is very low compared with that on the C-face. On the other hand, both the H2O molecule and the OH group are incorporated into the C-face interface, and the energy barrier for OH is similar to that for H2O. By comparing the calculated energy barriers for these reactants with the activation energies of oxide growth rate, we suggest the orientation-dependent rate-limiting processes during wet SiC oxidation.

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.

2016-01-01

(loose contact) the rate constants for a number of catalytic materials outline a volcano curve when plotted against their heats of oxygen chemisorption. However, the optima of the volcanoes correspond to different heats of chemisorption for the two contact situations. In both cases the activation...... 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...

Valence bond model potential energy surface for H4

International Nuclear Information System (INIS)

Silver, D.M.; Brown, N.J.

1980-01-01

Potential energy surfaces for the H 4 system are derived using the valence bond procedure. An ab initio evaluation of the valence bond energy expression is described and some of its numerical properties are given. Next, four semiempirical evaluations of the valence bond energy are defined and parametrized to yield reasonable agreement with various ab initio calculations of H 4 energies. Characteristics of these four H 4 surfaces are described by means of tabulated energy minima and equipotential contour maps for selected geometrical arrangements of the four nuclei

Hydrogen spillover in Pt-single-walled carbon nanotube composites: formation of stable C-H bonds.

Science.gov (United States)

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

2011-04-13

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

Computational Modeling of the Catalytic Cycle of Glutathione Peroxidase Nanomimic.

Science.gov (United States)

Kheirabadi, Ramesh; Izadyar, Mohammad

2016-12-29

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.

The Hydrogen Bonded Structures of Two 5-Bromobarbituric Acids and Analysis of Unequal C5–X and C5–X′ Bond Lengths (X = X′ = F, Cl, Br or Me in 5,5-Disubstituted Barbituric Acids

Directory of Open Access Journals (Sweden)

Thomas Gelbrich

2016-04-01

Full Text Available The crystal structure of the methanol hemisolvate of 5,5-dibromobarbituric acid (1MH displays an H-bonded layer structure which is based on N–H∙∙∙O=C, N–H∙∙∙O(MeOH and (MeOHO–H∙∙∙O interactions. The barbiturate molecules form an H-bonded substructure which has the fes topology. 5,5′-Methanediylbis(5-bromobarbituric acid 2, obtained from a solution of 5,5-dibromobarbituric acid in nitromethane, displays a N–H···O=C bonded framework of the sxd type. The conformation of the pyridmidine ring and the lengths of the ring substituent bonds C5–X and C5–X′ in crystal forms of 5,5-dibromobarbituric acid and three closely related analogues (X = X′ = Br, Cl, F, Me have been investigated. In each case, a conformation close to a C5-endo envelope is correlated with a significant lengthening of the axial C5–X′ in comparison to the equatorial C5–X bond. Isolated molecule geometry optimizations at different levels of theory confirm that the C5-endo envelope is the global conformational energy minimum of 5,5-dihalogenbarbituric acids. The relative lengthening of the axial bond is therefore interpreted as an inherent feature of the preferred envelope conformation of the pyrimidine ring, which minimizes repulsive interactions between the axial substituent and pyrimidine ring atoms.

C-H and C-C activation of n -butane with zirconium hydrides supported on SBA15 containing N-donor ligands: [(≡SiNH-)(≡SiX-)ZrH2], [(≡SiNH-)(≡SiX-)2ZrH], and[(≡SiN=)(≡SiX-)ZrH] (X = -NH-, -O-). A DFT study

KAUST Repository

Pasha, Farhan Ahmad; Bendjeriou-Sedjerari, Anissa; Huang, Kuo-Wei; Basset, Jean-Marie

2014-01-01

: [(≡SiNH-)(≡SiO-)ZrH2] (A), [(≡SiNH-)2ZrH2] (B), [(≡SiNH-)(≡SiO-) 2ZrH] (C), [(≡SiNH-)2(≡SiO-)ZrH] (D), [(≡SiN=)(≡Si-O-)ZrH] (E), and [(≡SiN=)(≡SiNH-)ZrH] (F). The roles of these hydrides have been investigated in C-H/C-C bond activation and cleavage

H-shaped supra-amphiphiles based on a dynamic covalent bond.

Science.gov (United States)

Wang, Guangtong; Wang, Chao; Wang, Zhiqiang; Zhang, Xi

2012-10-16

The imine bond, a kind of dynamic covalent bond, is used to bind two bolaform amphiphiles together with spacers, yielding H-shaped supra-amphiphiles. Micellar aggregates formed by the self-assembly of the H-shaped supra-amphiphiles are observed. When pH is tuned down from basic to slightly acidic, the benzoic imine bond can be hydrolyzed, leading to the dissociation of H-shaped supra-amphiphiles. Moreover, H-shaped supra-amphiphiles have a lower critical micelle concentration than their building blocks, which is very helpful in enhancing the stability of the benzoic imine bond being hydrolyzed by acid. The surface tension isotherms of the H-shaped supra-amphiphiles with different spacers indicate their twisty conformation at a gas-water interface. The study of H-shaped supra-amphiphiles can enrich the family of amphiphiles, and moreover, the pH-responsiveness may make them apply to controlled or targetable drug delivery in a biological environment.

AVE bond index in the H-bond of the Watson-Crick pairs

International Nuclear Information System (INIS)

Giambiagi, M.; Giambiagi, M.S. de; Barroso Filho, W.

1981-01-01

The normal Watson-Crick base pairs are treated as super-molecules. The properties of the electronic distribution along the N-H...Y bonds are studied in an all-valence-electrons calculation, through a bond index formula devised for non-orthogonal basis. Eletronic density diagrams of the adenine-uracil base pair are analysed. (Auhor) [pt

Selective sp3 C–H alkylation via polarity-match-based cross-coupling

Science.gov (United States)

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

2017-01-01

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 sequence1. 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. PMID:28636596

WD40 domain of Apc1 is critical for the coactivator-induced allosteric transition that stimulates APC/C catalytic activity.

Science.gov (United States)

Li, Qiuhong; Chang, Leifu; Aibara, Shintaro; Yang, Jing; Zhang, Ziguo; Barford, David

2016-09-20

The anaphase-promoting complex/cyclosome (APC/C) is a large multimeric cullin-RING E3 ubiquitin ligase that orchestrates cell-cycle progression by targeting cell-cycle regulatory proteins for destruction via the ubiquitin proteasome system. The APC/C assembly comprises two scaffolding subcomplexes: the platform and the TPR lobe that together coordinate the juxtaposition of the catalytic and substrate-recognition modules. The platform comprises APC/C subunits Apc1, Apc4, Apc5, and Apc15. Although the role of Apc1 as an APC/C scaffolding subunit has been characterized, its specific functions in contributing toward APC/C catalytic activity are not fully understood. Here, we report the crystal structure of the N-terminal domain of human Apc1 (Apc1N) determined at 2.2-Å resolution and provide an atomic-resolution description of the architecture of its WD40 (WD40 repeat) domain (Apc1(WD40)). To understand how Apc1(WD40) contributes to APC/C activity, a mutant form of the APC/C with Apc1(WD40) deleted was generated and evaluated biochemically and structurally. We found that the deletion of Apc1(WD40) abolished the UbcH10-dependent ubiquitination of APC/C substrates without impairing the Ube2S-dependent ubiquitin chain elongation activity. A cryo-EM structure of an APC/C-Cdh1 complex with Apc1(WD40) deleted showed that the mutant APC/C is locked into an inactive conformation in which the UbcH10-binding site of the catalytic module is inaccessible. Additionally, an EM density for Apc15 is not visible. Our data show that Apc1(WD40) is required to mediate the coactivator-induced conformational change of the APC/C that is responsible for stimulating APC/C catalytic activity by promoting UbcH10 binding. In contrast, Ube2S activity toward APC/C substrates is not dependent on the initiation-competent conformation of the APC/C.

Shear bond strength of one-step self-etch adhesives: pH influence

Science.gov (United States)

Poggio, Claudio; Beltrami, Riccardo; Scribante, Andrea; Colombo, Marco; Chiesa, Marco

2015-01-01

Background: The aim of this study was to compare the shear bond strength of four one-step self-etch adhesives with different pH values to enamel and dentin. Materials and Methods: In this in vitro study, 200 bovine permanent mandibular incisors were used. Four one-step self-etch adhesives with different pH values were tested both on enamel and on dentin: Adper™ Easy Bond Self-Etch Adhesive (pH = 0.8-1), Futurabond NR (pH=2), G-aenial Bond (pH = 1.5), Clearfil S3 Bond (pH = 2.7). After adhesive systems application, a nanohybrid composite resin was inserted into the bonded surface. The specimens were placed in a universal testing machine. The shear bond strength was performed at a cross-head speed of 1 mm/min until the sample rupture. The shear bond strength values (MPa) of the different groups were compared with analysis of variance after that Kolmogorov and Smirnov tests were applied to assess normality of distributions. P enamel shear bond strength, the highest shear bond strength values were reported with Futurabond NR (P adhesive systems showed lower shear bond strength values with significant differences between them (P 0.05). Conclusion: The pH values of adhesive systems did not influence significantly their shear bond strength to enamel or dentin. PMID:26005459

Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

Science.gov (United States)

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

2014-10-01

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.

Ultraviolet laser deposition of graphene thin films without catalytic layers

KAUST Repository

Sarath Kumar, S. R.; Alshareef, Husam N.

2013-01-01

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.

Ultraviolet laser deposition of graphene thin films without catalytic layers

KAUST Repository

Sarath Kumar, S. R.

2013-01-09

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.

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

Science.gov (United States)

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

2008-07-01

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 Pro(186), Leu(266), His(269), and the His(153) imidazole. The hydroxyl of Tyr(149) is also an integrated component of the chain, which leads to the hydroxyl of Tyr(154). Available data suggest that Tyr(154) functions as a final proton donor to the anionic alkylenzyme intermediate formed during catalysis. To investigate the role of the putative proton wire, mutants Y149F, H153F, and Y149F/H153F were constructed and purified. The structure of the Y149F mutant was solved by molecular replacement and refined to 2.0 A resolution. Comparison with the structure of wild-type StEH1 revealed only subtle structural differences. The hydroxyl group lost as a result of the mutation was replaced by a water molecule, thus maintaining a functioning hydrogen bond network in the proton wire. All mutants showed decreased catalytic efficiencies with the R,R-enantiomer of trans-stilbene oxide, whereas with the S,S-enantiomer, k (cat)/K (M) was similar or slightly increased compared with the wild-type reactions. k (cat) for the Y149F mutant with either TSO enantiomer was increased; thus the lowered enzyme efficiencies were due to increases in K (M). Thermal inactivation studies revealed that the mutated enzymes were more sensitive to elevated temperatures than the wild-type enzyme. Hence, structural alterations affecting the hydrogen bond chain caused increases in k (cat) but lowered thermostability.

Construction of Polarized Carbon-Nickel Catalytic Surfaces for Potent, Durable, and Economic Hydrogen Evolution Reactions.

Science.gov (United States)

Zhou, Min; Weng, Qunhong; Popov, Zakhar I; Yang, Yijun; Antipina, Liubov Yu; Sorokin, Pavel B; Wang, Xi; Bando, Yoshio; Golberg, Dmitri

2018-05-22

Electrocatalytic hydrogen evolution reaction (HER) in alkaline solution is hindered by its sluggish kinetics toward water dissociation. Nickel-based catalysts, as low-cost and effective candidates, show great potentials to replace platinum (Pt)-based materials in the alkaline media. The main challenge regarding this type of catalysts is their relatively poor durability. In this work, we conceive and construct a charge-polarized carbon layer derived from carbon quantum dots (CQDs) on Ni 3 N nanostructure (Ni 3 N@CQDs) surfaces, which simultaneously exhibit durable and enhanced catalytic activity. The Ni 3 N@CQDs shows an overpotential of 69 mV at a current density of 10 mA cm -2 in a 1 M KOH aqueous solution, lower than that of Pt electrode (116 mV) at the same conditions. Density functional theory (DFT) simulations reveal that Ni 3 N and interfacial oxygen polarize charge distributions between originally equal C-C bonds in CQDs. The partially negatively charged C sites become effective catalytic centers for the key water dissociation step via the formation of new C-H bond (Volmer step) and thus boost the HER activity. Furthermore, the coated carbon is also found to protect interior Ni 3 N from oxidization/hydroxylation and therefore guarantees its durability. This work provides a practical design of robust and durable HER electrocatalysts based on nonprecious metals.

Catalytic Deoxygenation of Fatty Acids: Elucidation of the Inhibition Process

NARCIS (Netherlands)

Hollak, S.A.W.; Jong, de K.P.; Es, van D.S.

2014-01-01

Catalytic deoxygenation of unsaturated fatty acids in the absence of H2 is known to suffer from significant catalyst inhibition. Thus far, no conclusive results have been reported on the cause of deactivation. Here we show that CC double bonds present in the feed or the products dramatically reduce

Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp2 and sp3 C-H Bonds

Science.gov (United States)

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

2013-01-01

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

Electronic structure of the alkyne-bridged dicobalt hexacarbonyl complex Co(2) micro-C(2)H(2) (CO)(6): evidence for singlet diradical character and implications for metal-metal bonding.

Science.gov (United States)

Platts, James A; Evans, Gareth J S; Coogan, Michael P; Overgaard, Jacob

2007-08-06

A series of ab initio calculations are presented on the alkyne-bridged dicobalt hexacarbonyl cluster Co2 micro-C2H2 (CO)6, indicating that this compound has substantial multireference character, which we interpret as evidence of singlet diradical behavior. As a result, standard theoretical methods such as restricted Hartree-Fock (RHF) or Kohn-Sham (RKS) density functional theory cannot properly describe this compound. We have therefore used complete active space (CAS) methods to explore the bonding in and spectroscopic properties of Co2 micro-C2H2 (CO)6. CAS methods identify significant population of a Co-Co antibonding orbital, along with Co-pi* back-bonding, and a relatively large singlet-triplet energy splitting. Analysis of the electron density and related quantities, such as energy densities and atomic overlaps, indicates a small but significant amount of covalent bonding between cobalt centers.

Hydrogenation of the Exocyclic Olefinic Bond at C-16/C-17 Position of ent-Kaurane Diterpene Glycosides of Stevia rebaudiana Using Various Catalysts

Science.gov (United States)

Chaturvedula, Venkata Sai Prakash; Prakash, Indra

2013-01-01

Catalytic hydrogenation of the exocyclic double bond present between C16 and C17 carbons of the four ent-kaurane diterpene glycosides namely rebaudioside A, rebaudioside B, rebaudioside C, and rebaudioside D isolated from Stevia rebaudiana has been carried out using Pt/C, Pd(OH)2, Rh/C, Raney Ni, PtO2, and 5% Pd/BaCO3 to their corresponding dihydro derivatives with 17α and 17β methyl group isomers. Reactions were performed using the above-mentioned catalysts with the solvents methanol, water, and ethanol/water (8:2) under various conditions. Synthesis of reduced steviol glycosides was performed using straightforward chemistry and their structures were characterized on the basis of 1D and 2D NMR spectral data, including a comparison with reported spectral data. PMID:23896597

Hydrogenation of the Exocyclic Olefinic Bond at C-16/C-17 Position of ent-Kaurane Diterpene Glycosides of Stevia rebaudiana Using Various Catalysts

Directory of Open Access Journals (Sweden)

Indra Prakash

2013-07-01

Full Text Available Catalytic hydrogenation of the exocyclic double bond present between C16 and C17 carbons of the four ent-kaurane diterpene glycosides namely rebaudioside A, rebaudioside B, rebaudioside C, and rebaudioside D isolated from Stevia rebaudiana has been carried out using Pt/C, Pd(OH2, Rh/C, Raney Ni, PtO2, and 5% Pd/BaCO3 to their corresponding dihydro derivatives with 17α and 17β methyl group isomers. Reactions were performed using the above-mentioned catalysts with the solvents methanol, water, and ethanol/water (8:2 under various conditions. Synthesis of reduced steviol glycosides was performed using straightforward chemistry and their structures were characterized on the basis of 1D and 2D NMR spectral data, including a comparison with reported spectral data.

Metal modified tungsten carbide (WC) for catalytic and electrocatalytic applications

Science.gov (United States)

Mellinger, Zachary J.

One of the major challenges in the commercialization of proton exchange membrane fuel cells (PEMFC) is the cost, and low CO tolerance of the anode electrocatalyst material. The anode typically requires a high loading of precious metal electrocatalyst (Pt or Pt--Ru) to obtain a useful amount of electrical energy from the electrooxidation of methanol (CH3OH) or ethanol (C2H5OH). The complete electro--oxidation of methanol or ethanol on these catalysts produces strongly adsorbed CO on the surface, which reduces the activity of the Pt or Pt--Ru catalysts. Another major disadvantage of these electrocatalyst components is the scarcity and consequently high price of both Pt and Ru. Tungsten monocarbide (WC) has shown similar catalytic properties to Pt, leading to the utilization of WC and metal modified WC as replacements to Pt and Pt--Ru. In this thesis we investigated WC and Pt--modified WC as a potentially more CO--tolerant electrocatalysts as compared to pure Pt. These catalysts would reduce or remove the high loading of Pt used industrially. The binding energy of CO, estimated using temperature programmed desorption, is weaker on WC and Pt/WC than on Pt, suggesting that it should be easier to oxidize CO on WC and Pt/WC. This hypothesis was verified using cyclic voltammetry to compare the electro--oxidation of CO on WC, Pt/WC, and Pt supported on carbon substrates, which showed a lower voltage for the onset of oxidation of CO on WC and Pt/WC than on Pt. After observing these improved properties on the Pt/WC catalysts, we decided to expand our studies to investigate Pd--modified WC as Pd is less expensive than Pt and has shown more ideal properties for alcohol electrocatalysis in alkaline media. Pd/WC showed a lower binding energy of CO than both its parent metal Pd as well as Pt. Then, density functional theory (DFT) calculations were performed to determine how the presence of Pd affected the bonding of methanol and ethanol on the WC surface. The DFT studies showed

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.

2001-02-01

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

Synthesis of propargylic and allenic carbamates via the C-H amination of alkynes.

Science.gov (United States)

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

2012-01-06

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

Discovering H-bonding rules in crystals with inductive logic programming.

Science.gov (United States)

Ando, Howard Y; Dehaspe, Luc; Luyten, Walter; Van Craenenbroeck, Elke; Vandecasteele, Henk; Van Meervelt, Luc

2006-01-01

In the domain of crystal engineering, various schemes have been proposed for the classification of hydrogen bonding (H-bonding) patterns observed in 3D crystal structures. In this study, the aim is to complement these schemes with rules that predict H-bonding in crystals from 2D structural information only. Modern computational power and the advances in inductive logic programming (ILP) can now provide computational chemistry with the opportunity for extracting structure-specific rules from large databases that can be incorporated into expert systems. ILP technology is here applied to H-bonding in crystals to develop a self-extracting expert system utilizing data in the Cambridge Structural Database of small molecule crystal structures. A clear increase in performance was observed when the ILP system DMax was allowed to refer to the local structural environment of the possible H-bond donor/acceptor pairs. This ability distinguishes ILP from more traditional approaches that build rules on the basis of global molecular properties.

Ferroelectric phase transition in hydrogen-bonded 2-aminopyridine phosphate (NC sub 4 H sub 4 NH sub 2)centre dot H sub 3 PO sub 4

CERN Document Server

Czapla, Z; Waskowska, A

2003-01-01

A new crystal of 2-aminopyridine phosphate (NC sub 4 H sub 4 NH sub 2)centre dot H sub 3 PO sub 4 has been grown and its x-ray structure and physical properties were studied. At room temperature the crystals are monoclinic, space group C2/c. The flat 2-aminopyridine cations are hydrogen bonded to the anionic [PO sub 4 ] groups. The interesting feature of the crystal structure is the three-dimensional network of hydrogen bonds including, among others, two strong, symmetrical O centre dot centre dot centre dot H, H centre dot centre dot centre dot O interactions with disordered proton locations. Symmetrically related PO sub 4 anions linked through these protons form infinite (PO sub 4) subinfinity chains along the crystal a-axis. The anomalies in the temperature dependence of the electric permittivity showed that the crystal undergoes ferroelectric phase transition at T sub c = 103.5 K. The spontaneous polarization takes place along the crystal a-axis, being parallel to the chains of the hydrogen-bonded PO sub ...

Alignment of paired molecules of C60 within a hexagonal platform networked through hydrogen-bonds.

Science.gov (United States)

Hisaki, Ichiro; Nakagawa, Shoichi; Sato, Hiroyasu; Tohnai, Norimitsu

2016-07-28

We demonstrate, for the first time, that a hydrogen-bonded low-density organic framework can be applied as a platform to achieve periodic alignment of paired molecules of C60, which is the smallest example of a finite-numbered cluster of C60. The framework is a layered assembly of a hydrogen-bonded 2D hexagonal network (LA-H-HexNet) composed of dodecadehydrotribenzo[18]annulene derivatives.

Catalytic Hydrodechlorination of Trichlorobenzenes with Pd(PhenCl2 as Catalyst Precursor

Directory of Open Access Journals (Sweden)

Guanlin Zhang

2015-01-01

Full Text Available We reported the catalytic hydrodechlorination (HDC of trichlorobenzenes by an organometallic compound Pd(PhenCl2 as a catalyst precursor. The catalyst precursor was prepared by chemical coordination reaction and characterized by FTIR and 1H NMR techniques. The HDC performance of Pd(PhenCl2 as catalyst precursor was evaluated on 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes (TCBs. All TCBs could be converted to dechlorination products with high conversion. Products distribution was closely related with the substrate structures and C-Cl bond energies. A reasonable reaction mechanism was also proposed.

Ruthenium(II)-Catalyzed C-H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate-Controlled Synthesis of Indoles and 3H-Indoles.

Science.gov (United States)

Li, Yunyun; Qi, Zisong; Wang, He; Yang, Xifa; Li, Xingwei

2016-09-19

Indoles are an important structural motif that is commonly found in biologically active molecules. In this work, conditions for divergent couplings between imidamides and acceptor-acceptor diazo compounds were developed that afforded NH indoles and 3H-indoles under ruthenium catalysis. The coupling of α-diazoketoesters afforded NH indoles by cleavage of the C(N2 )-C(acyl) bond whereas α-diazomalonates gave 3H-indoles by C-N bond cleavage. This reaction constitutes the first intermolecular coupling of diazo substrates with arenes by ruthenium-catalyzed C-H activation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-isothermal synergetic catalytic effect of TiF{sub 3} and Nb{sub 2}O{sub 5} on dehydrogenation high-energy ball milled MgH{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Zhang, Tiebang, E-mail: tiebangzhang@nwpu.edu.cn; Hou, Xiaojiang; Hu, Rui; Kou, Hongchao; Li, Jinshan

2016-11-01

MgH{sub 2}-M (M = TiF{sub 3} or Nb{sub 2}O{sub 5} or both of them) composites prepared by high-energy ball milling are used in this work to illustrate the dehydrogenation behavior of MgH{sub 2} with the addition of catalysts. The phase compositions, microstructures, particle morphologies and distributions of MgH{sub 2} with catalysts have been evaluated. The non-isothermal synergetic catalytic-dehydrogenation effect of TiF{sub 3} and Nb{sub 2}O{sub 5} evaluated by differential scanning calorimetry gives the evidences that the addition of catalysts is an effective strategy to destabilize MgH{sub 2} and reduce hydrogen desorption temperatures and activation energies. Depending on additives, the desorption peak temperatures of catalyzed MgH{sub 2} reduce from 417 °C to 341 °C for TiF{sub 3} and from 417 °C to 336 °C for Nb{sub 2}O{sub 5}, respectively. The desorption peak temperature reaches as low as 310 °C for MgH{sub 2} catalyzed by TiF{sub 3} coupling with Nb{sub 2}O{sub 5}. The non-isothermal synergetic catalytic effect of TiF{sub 3} and Nb{sub 2}O{sub 5} is mainly attributed to electronic exchange reactions with hydrogen molecules, which improve the recombination of hydrogen atoms during dehydrogenation process of MgH{sub 2}. - Highlights: • Catalytic surface for MgH{sub 2} is achieved by high-energy ball milling. • Non-isothermal dehydrogenation behavior of MgH{sub 2} with TiF{sub 3} and/or Nb{sub 2}O{sub 5} is illustrated. • Dehydrogenation activation energies of synergetic catalyzed MgH{sub 2} are obtained. • Synergetic catalytic-dehydrogenation mechanism of TiF{sub 3} and Nb{sub 2}O{sub 5} is proposed.

Bonding and structure of copper nitrenes.

Science.gov (United States)

Cundari, Thomas R; Dinescu, Adriana; Kazi, Abul B

2008-11-03

Copper nitrenes are of interest as intermediates in the catalytic aziridination of olefins and the amination of C-H bonds. However, despite advances in the isolation and study of late-transition-metal multiply bonded complexes, a bona fide structurally characterized example of a terminal copper nitrene has, to our knowledge, not been reported. In anticipation of such a report, terminal copper nitrenes are studied from a computational perspective. The nitrene complexes studied here are of the form (beta-diketiminate)Cu(NPh). Density functional theory (DFT), complete active space self-consistent-field (CASSCF) electronic structure techniques, and hybrid quantum mechanical/molecular mechanical (QM/MM) methods are employed to study such species. While DFT methods indicate that a triplet (S = 1) is the ground state, CASSCF calculations indicate that a singlet (S = 0) is the ground state, with only a small energy gap between the singlet and triplet. Moreover, the ground-state (open-shell) singlet copper nitrene is found to be highly multiconfigurational (i.e., biradical) and to possess a bent geometry about the nitrene nitrogen, contrasting with the linear nitrene geometry of the triplet copper nitrenes. CASSCF calculations also reveal the existence of a closed-shell singlet state with some degree of multiple bonding character for the copper-nitrene bond.

The electronic donation and frequency shifts on the YCCH⋯BH₄⁻ boron-bonded complexes (Y=H, CH₃, CF₃ and CCl₃).

Science.gov (United States)

Pordeus, Renato Q; Rego, Danilo G; Oliveira, Boaz G

2015-06-15

In this theoretical work, the tetrahydroborate ion (BH4(-)) was used as proton acceptor in the formation of the YCC-H⋯BH4(-) complexes (Y=H, CH3, CCl3 and CF3). Using B3LYP/6-311++G(d,p) level of theory, the results of structure corroborate with the analyses of infrared spectra showing that the changes in the bond lengths are in good agreement with the frequency shifts of the HCC-H, H3CCC-H, Cl3CCC-H and F3CCC-H proton donors. Based on the calculations carried out by the Quantum Theory of Atoms in Molecules (QTAIM), the reductions of electronic density corroborate with the red shifts in the frequencies of the C-H bonds. In addition to that, the C-H bonds are polarized because the contributions of s orbital diminish whereas of p increase. In line with this, the variations on the atomic radii computed via QTAIM calculations show that carbon outweigh hydrogen as follows (ΔrC>ΔrH). This scenario is indirectly supported by the Bent's rule of the chemical bonding. Although the interaction energies (corrected with BSSE and ZPE) vary between -19 and -67 kJ mol(-1), these complexes interact without covalent character. Copyright © 2015 Elsevier B.V. All rights reserved.

Crystallographic and infrared spectroscopic study of bond distances in Ln[Fe(CN)6].4H2O (Ln=lanthanide)

International Nuclear Information System (INIS)

Zhou Xianju; Wong, W.-T.; Faucher, Michele D.; Tanner, Peter A.

2008-01-01

Along with crystallographic data of Ln[Fe(CN) 6 ].4H 2 O (Ln=lanthanide), the infrared spectra are reassigned to examine bond length trends across the series of Ln. The changes in mean Ln-O, Ln-N, C≡N and Fe-C distances are discussed and the bond natures of Ln-N and Ln-O are studied by bond length linear or quadratic fitting and comparisons with relevant ionic radii. The two different C≡N bond distances have been simulated by the covalo-electrostatic model. - Graphical abstract: Crystallographic and FTIR data for Ln[Fe(CN) 6 ].4H 2 O enable the changes in Ln-O, Ln-N, C≡N and Fe-C distances to be determined and modeled across the lanthanide series

Catalytic-site mapping of pyruvate formate lyase. Hypophosphite reaction on the acetyl-enzyme intermediate affords carbon-phosphorus bond synthesis (1-hydroxyethylphosphonate).

Science.gov (United States)

Plaga, W; Frank, R; Knappe, J

1988-12-15

Pyruvate formate-lyase of Escherichia coli cells, a homodimeric protein of 2 x 85 kDa, is distinguished by the property of containing a stable organic free radical (g = 2.0037) in its resting state. The enzyme (E-SH) achieves pyruvate conversion to acetyl-CoA via two distinct half-reactions (E-SH + pyruvate in equilibrium E-S-acetyl + formate; E-S-acetyl + CoA in equilibrium E-SH + acetyl-CoA), the first of which has been proposed to involve reversible homolytic carbon-carbon bond cleavage [J. Knappe et al. (1984) Proc. Natl Acad. Sci. USA 81, 1332-1335]. Present studies identified Cys-419 as the covalent-catalytic cysteinyl residue via CNBr fragmentation of E-S-[14C]acetyl and radio-sequencing of the isolated peptide CB-Ac (amino acid residues 406-423). Reaction of the formate analogue hypophosphite with E-S-acetyl was investigated and found to produce 1-hydroxyethylphosphonate with a thioester linkage to the adjacent Cys-418. The structure was determined from the chymotryptic peptide CH-P (amino acid residues 415-425), using 31P-NMR spectroscopy (delta = 44 ppm) and by chemical characterisation through degradation into 1-hydroxyethylphosphonate with phosphodiesterase or bromine. This novel P-C-bond synthesis involves the enzyme-based free radical and is proposed to resemble the physiological C-C-bond synthesis (pyruvate production) from formate and E-S-acetyl. These findings are interpreted as proof of a radical mechanism for the action of pyruvate formate-lyase. The central Cys-418/Cys-419 pair of the active site shows a distinctive thiolate property even in the inactive (nonradical) form of the enzyme, as determined using an iodoacetate probe.

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

Science.gov (United States)

Misal Castro, Luis C; Chatani, Naoto

2014-04-14

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.

Direct Carboxylation of the Diazo Group ipso-C(sp2)-H bond with Carbon Dioxide: Access to Unsymmetrical Diazomalonates and Derivatives.

Science.gov (United States)

Liu, Qianyi; Li, Man; Xiong, Rui; Mo, Fanyang

2017-12-15

The direct carboxylation of the ipso-C(sp 2 )-H bond of a diazo compound with carbon dioxide under mild reaction conditions is described. This method is transition-metal-free, uses a weak base, and proceeds at ambient temperature under atmospheric pressure in carbon dioxide. The carboxylation exhibits high reactivity and is amenable to subsequent diversification. A series of unsymmetrical 1,3-diester/keto/amide diazo compounds are obtained with moderate to excellent yields (up to 99%) with good functional group compatibility.

Observation of H-bond mediated 3hJH2H3coupling constants across Watson-Crick AU base pairs in RNA

International Nuclear Information System (INIS)

Luy, Burkhard; Richter, Uwe; DeJong, Eric S.; Sorensen, Ole W.; Marino, John P.

2002-01-01

3h J H2H3 trans-hydrogen bond scalar coupling constants have been observed for the first time in Watson-Crick AU base pairs in uniformly 15 N-labeled RNA oligonucleotides using a new 2h J NN -HNN-E. COSY experiment. The experiment utilizes adenosine H2 (AH2) for original polarization and detection, while employing 2h J NN couplings for coherence transfer across the hydrogen bonds (H-bonds). The H3 protons of uracil bases are unperturbed throughout the experiment so that these protons appear as passive spins in E. COSY patterns. 3h J H2H3 coupling constants can therefore be accurately measured in the acquisition dimension from the displacement of the E. COSY multiplet components, which are separated by the relatively large 1 J H3N3 coupling constants in the indirect dimension of the two-dimensional experiment. The 3h J H2H3 scalar coupling constants determined for AU base pairs in the two RNA hairpins examined here have been found to be positive and range in magnitude up to 1.8 Hz. Using a molecular fragment representation of an AU base pair, density functional theory/finite field perturbation theory (DFT/FPT) methods have been applied to attempt to predict the relative contributions of H-bond length and angular geometry to the magnitude of 3h J H2H3 coupling constants. Although the DFT/FPT calculations did not reproduce the full range of magnitude observed experimentally for the 3h J H2H3 coupling constants, the calculations do predict the correct sign and general trends in variation in size of these coupling constants. The calculations suggest that the magnitude of the coupling constants depends largely on H-bond length, but can also vary with differences in base pair geometry. The dependency of the 3h J H2H3 coupling constant on H-bond strength and geometry makes it a new probe for defining base pairs in NMR studies of nucleic acids

Catalytic oligomerization of terminal alkynes promoted by organo-f-complexes

International Nuclear Information System (INIS)

Straub, T.; Haskel, A.; Eisen, M.S.

1995-01-01

Organoactinides of the type Cp* 2 AcMe 2 (Cp*=C 5 Me 5 ; Ac=Th, U) are active catalyst precursors for the oligomerization of terminal alkynes HC triple-bond CR (R=alkyl, aryl, SiMe 3 ). The regioselectivity and the extent of oligomerization strongly depend on the alkyne substituent R, whereas the catalytic reactivity is similar for 1 and 2. In the presence of one of these organoactinides, for example, HCCSiMe 3 regioselectively oligomerizes to the head-to-tail dimer 3 (5%) and the trimer 4 (95%). 1 and 2 react with the terminal alkynes, releasing methane, to the corresponding bisacetylide complexes which are active species and in the catalytic reactions. The bisacetylide complex (η 5 -C 5 Me 5 ) 2 U(CCPh) 2 was identified by proton NMR spectroscopy. Subsequent insertion of alkyne molecules in the actinide-carbon σ-bonds leads to the formation of actinide-alkenyl complexes. The turnover limiting step is the release of the organic oligomer from the actinide-organyl complex. A species of the latter has been spectroscopically characterized in the trimerization reaction of HCCSiMe 3 . In this poster, the catalytic reactivity of the actinide alkyls 1 and 2 with various mono-substituted alkynes as well as the spectroscopic characterization of the key organometallic intermediate complexes in the catalytic cycle and a detailed mechanistic discussion are given

Rhodium (II) carbene C-H insertion in water and catalyst reuse; Insercao C-H de carbenoides de rodio em agua e reutilizacao do catalisador

Energy Technology Data Exchange (ETDEWEB)

Candeias, Nuno R.; Gois, Pedro M.P.; Afonso, Carlos A.M. [Instituto Superior Tecnico, Lisboa (Portugal)]. E-mail: carlosafonso@ist.utl.pt

2007-07-01

A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II) catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonyl acetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh{sub 2}(OAc){sub 4}. The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization. (author)

H/D Isotope Effects in Hydrogen Bonded Systems

Directory of Open Access Journals (Sweden)

Aleksander Filarowski

2013-04-01

Full Text Available An extremely strong H/D isotope effect observed in hydrogen bonded A-H…B systems is connected with a reach diversity of the potential shape for the proton/deuteron motion. It is connected with the anharmonicity of the proton/deuteron vibrations and of the tunneling effect, particularly in cases of short bridges with low barrier for protonic and deuteronic jumping. Six extreme shapes of the proton motion are presented starting from the state without possibility of the proton transfer up to the state with a full ionization. The manifestations of the H/D isotope effect are best reflected in the infra-red absorption spectra. A most characteristic is the run of the relationship between the isotopic ratio nH/nD and position of the absorption band shown by using the example of NHN hydrogen bonds. One can distinguish a critical range of correlation when the isotopic ratio reaches the value of ca. 1 and then increases up to unusual values higher than . The critical range of the isotope effect is also visible in NQR and NMR spectra. In the critical region one observes a stepwise change of the NQR frequency reaching 1.1 MHz. In the case of NMR, the maximal isotope effect is reflected on the curve presenting the dependence of Δd (1H,2H on d (1H. This effect corresponds to the range of maximum on the correlation curve between dH and ΔpKa that is observed in various systems. There is a lack in the literature of quantitative information about the influence of isotopic substitution on the dielectric properties of hydrogen bond except the isotope effect on the ferroelectric phase transition in some hydrogen bonded crystals.

Engineered disulfide bonds increase active-site local stability and reduce catalytic activity of a cold-adapted alkaline phosphatase.

Science.gov (United States)

Asgeirsson, Bjarni; Adalbjörnsson, Björn Vidar; Gylfason, Gudjón Andri

2007-06-01

Alkaline phosphatase is an extracellular enzyme that is membrane-bound in eukaryotes but resides in the periplasmic space of bacteria. It normally carries four cysteine residues that form two disulfide bonds, for instance in the APs of Escherichia coli and vertebrates. An AP variant from a Vibrio sp. has only one cysteine residue. This cysteine is second next to the nucleophilic serine in the active site. We have individually modified seven residues to cysteine that are on two loops predicted to be within a 5 A radius. Four of them formed a disulfide bond to the endogenous cysteine. Thermal stability was monitored by circular dichroism and activity measurements. Global stability was similar to the wild-type enzyme. However, a significant increase in heat-stability was observed for the disulfide-containing variants using activity as a measure, together with a large reduction in catalytic rates (k(cat)) and a general decrease in Km values. The results suggest that a high degree of mobility near the active site and in the helix carrying the endogenous cysteine is essential for full catalytic efficiency in the cold-adapted AP.

Catalytic water co-existing with a product peptide in the active site of HIV-1 protease revealed by X-ray structure analysis.

Science.gov (United States)

Prashar, Vishal; Bihani, Subhash; Das, Amit; Ferrer, Jean-Luc; Hosur, Madhusoodan

2009-11-17

It is known that HIV-1 protease is an important target for design of antiviral compounds in the treatment of Acquired Immuno Deficiency Syndrome (AIDS). In this context, understanding the catalytic mechanism of the enzyme is of crucial importance as transition state structure directs inhibitor design. Most mechanistic proposals invoke nucleophilic attack on the scissile peptide bond by a water molecule. But such a water molecule coexisting with any ligand in the active site has not been found so far in the crystal structures. We report here the first observation of the coexistence in the active site, of a water molecule WAT1, along with the carboxyl terminal product (Q product) peptide. The product peptide has been generated in situ through cleavage of the full-length substrate. The N-terminal product (P product) has diffused out and is replaced by a set of water molecules while the Q product is still held in the active site through hydrogen bonds. The position of WAT1, which hydrogen bonds to both the catalytic aspartates, is different from when there is no substrate bound in the active site. We propose WAT1 to be the position from where catalytic water attacks the scissile peptide bond. Comparison of structures of HIV-1 protease complexed with the same oligopeptide substrate, but at pH 2.0 and at pH 7.0 shows interesting changes in the conformation and hydrogen bonding interactions from the catalytic aspartates. The structure is suggestive of the repositioning, during substrate binding, of the catalytic water for activation and subsequent nucleophilic attack. The structure could be a snap shot of the enzyme active site primed for the next round of catalysis. This structure further suggests that to achieve the goal of designing inhibitors mimicking the transition-state, the hydrogen-bonding pattern between WAT1 and the enzyme should be replicated.

Copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines: synthesis of imidazopyridine derivatives.

Science.gov (United States)

Yu, Jipan; Jin, Yunhe; Zhang, Hao; Yang, Xiaobo; Fu, Hua

2013-12-02

A novel, efficient, and practical method for the synthesis of imidazopyridine derivatives has been developed through the copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines with N-(alkylidene)-4H-1,2,4-triazol-4-amines. The procedure occurs by cleavage of the N-N bond in the N-(alkylidene)-4H-1,2,4-triazol-4-amines and activation of an aryl C-H bond in the substituted pyridines. This is the first example of the preparation of imidazopyridine derivatives by using pyridines as the substrates by transition-metal-catalyzed C-H functionalization. This method should provide a novel and efficient strategy for the synthesis of other nitrogen heterocycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural Characterization of N-Alkylated Twisted Amides: Consequences for Amide Bond Resonance and N-C Cleavage.

Science.gov (United States)

Hu, Feng; Lalancette, Roger; Szostak, Michal

2016-04-11

Herein, we describe the first structural characterization of N-alkylated twisted amides prepared directly by N-alkylation of the corresponding non-planar lactams. This study provides the first experimental evidence that N-alkylation results in a dramatic increase of non-planarity around the amide N-C(O) bond. Moreover, we report a rare example of a molecular wire supported by the same amide C=O-Ag bonds. Reactivity studies demonstrate rapid nucleophilic addition to the N-C(O) moiety of N-alkylated amides, indicating the lack of n(N) to π*(C=O) conjugation. Most crucially, we demonstrate that N-alkylation activates the otherwise unreactive amide bond towards σ N-C cleavage by switchable coordination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic combustion of the retentate gas from a CO2/H2 separation membrane reactor for further CO2 enrichment and energy recovery

International Nuclear Information System (INIS)

Hwang, Kyung-Ran; Park, Jin-Woo; Lee, Sung-Wook; Hong, Sungkook; Lee, Chun-Boo; Oh, Duck-Kyu; Jin, Min-Ho; Lee, Dong-Wook; Park, Jong-Soo

2015-01-01

The CCR (catalytic combustion reaction) of the retentate gas, consisting of 90% CO 2 and 10% H 2 obtained from a CO 2 /H 2 separation membrane reactor, was investigated using a porous Ni metal catalyst in order to recover energy and further enrich CO 2 . A disc-shaped porous Ni metal catalyst, namely Al[0.1]/Ni, was prepared by a simple method and a compact MCR (micro-channel reactor) equipped with a catalyst plate was designed for the CCR. CO 2 and H 2 concentrations of 98.68% and 0.46%, respectively, were achieved at an operating temperature of 400 °C, GHSV (gas-hourly space velocity) of 50,000 h −1 and a H 2 /O 2 ratio (R/O) of 2 in the unit module. In the case of the MCR, a sheet of the Ni metal catalyst was easily installed along with the other metal plates and the concentration of CO 2 in the retentate gas increased up to 96.7%. The differences in temperatures measured before and after the CCR were 31 °C at the product outlet and 19 °C at the N 2 outlet in the MCR. The disc-shaped porous metal catalyst and MCR configuration used in this study exhibit potential advantages, such as high thermal transfer resulting in improved energy recovery rate, simple catalyst preparation, and easy installation of the catalyst in the MCR. - Highlights: • The catalytic combustion of a retentate gas obtained from the H 2 /CO 2 separation membrane. • A disc-shaped porous nickel metal catalyst and a micro-channel reactor for catalytic hydrogen combustion. • CO 2 enrichment up to 98.68% at 400 °C, 50,000 h −1 and H 2 /O 2 ratio of 2.

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)

2015-03-03

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

Ligand-enabled ortho-C–H olefination of phenylacetic amides with unactivated alkenes† †Electronic supplementary information (ESI) available: Data for new compounds and experimental procedures. See DOI: 10.1039/c7sc04827k

Science.gov (United States)

Lu, Ming-Zhu; Chen, Xing-Rong; Xu, Hui

2017-01-01

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(sp2)–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. PMID:29675177

Generation and reactivity of putative support systems, Ce-Al neutral binary oxide nanoclusters: CO oxidation and C-H bond activation

Science.gov (United States)

Wang, Zhe-Chen; Yin, Shi; Bernstein, Elliot R.

2013-11-01

Both ceria (CeO2) and alumina (Al2O3) are very important catalyst support materials. Neutral binary oxide nanoclusters (NBONCs), CexAlyOz, are generated and detected in the gas phase and their reactivity with carbon monoxide (CO) and butane (C4H10) is studied. The very active species CeAlO4• can react with CO and butane via O atom transfer (OAT) and H atom transfer (HAT), respectively. Other CexAlyOz NBONCs do not show reactivities toward CO and C4H10. The structures, as well as the reactivities, of CexAlyOz NBONCs are studied theoretically employing density functional theory (DFT) calculations. The ground state CeAlO4• NBONC possesses a kite-shaped structure with an OtCeObObAlOt configuration (Ot, terminal oxygen; Ob, bridging oxygen). An unpaired electron is localized on the Ot atom of the AlOt moiety rather than the CeOt moiety: this Ot centered radical moiety plays a very important role for the reactivity of the CeAlO4• NBONC. The reactivities of Ce2O4, CeAlO4•, and Al2O4 toward CO are compared, emphasizing the importance of a spin-localized terminal oxygen for these reactions. Intramolecular charge distributions do not appear to play a role in the reactivities of these neutral clusters, but could be important for charged isoelectronic BONCs. DFT studies show that the reaction of CeAlO4• with C4H10 to form the CeAlO4H•C4H9• encounter complex is barrierless. While HAT processes have been previously characterized for cationic and anionic oxide clusters, the reported study is the first observation of a HAT process supported by a ground state neutral oxide cluster. Mechanisms for catalytic oxidation of CO over surfaces of AlxOy/MmOn or MmOn/AlxOy materials are proposed consistent with the presented experimental and theoretical results.

Deuterium isotope effects on 13C chemical shifts of 10-Hydroxybenzo[h]quinolines

DEFF Research Database (Denmark)

Hansen, Poul Erik; Kamounah, Fadhil S.; Gryko, Daniel T.

2013-01-01

Deuterium isotope effects on 13C-NMR chemical shifts are investigated in a series of 10-hydroxybenzo[h]quinolines (HBQ’s) The OH proton is deuteriated. The isotope effects on 13C chemical shifts in these hydrogen bonded systems are rather unusual. The formal four-bond effects are found to be nega...

Relation between frequency and H bond length in heavy water: Towards the understanding of the unusual properties of H bond dynamics in nanoporous media

International Nuclear Information System (INIS)

Pommeret, Stanislas; Leicknam, Jean-Claude; Bratos, Savo; Musat, Raluca; Renault, Jean Philippe

2009-01-01

The published work on H bond dynamics mainly refers to diluted solutions HDO/D 2 O rather than to normal water. The reasons for this choice are both theoretical and experimental. Mechanical isolation of the OH vibrator eliminating the resonant energy transfer makes it a better probe of the local H bond network, while the dilution in heavy water reduces the infrared absorption, which permits the use of thicker experimental cells. The isotopic substitution does not alter crucially the nature of the problem. The length r of an OH . . . O group is statistically distributed over a large interval comprised between 2.7 and 3.2 A with a mean value r 0 = 2.86 A. Liquid water may thus be viewed as a mixture of hydrogen bonds of different length. Two important characteristics of hydrogen bonding must be mentioned. (i) The OH stretching vibrations are strongly affected by this interaction. The shorter the length r of the hydrogen bond, the strongest the H bond link and the lower is its frequency ω: the covalent OH bond energy is lent to the OH. . .O bond and reinforces the latter. A number of useful relationships between ω and r were published to express this correlation. The one adopted in our previous work is the relationship due to Mikenda. (ii) Not only the OH vibrations, but also the HDO rotations are influenced noticeably by hydrogen bonding. This is due to steric forces that hinder the HDO rotations. As they are stronger in short than in long hydrogen bonds, rotations are slower in the first case than in the second. This effect was only recently discovered, but its existence is hardly to be contested. In the present contribution, we want to revisit the relationship between the frequency of the OH vibrator and the distance OH. . .O.

C-C bond formation in the intramolecular Diels-Alder reaction of triene amides.

Science.gov (United States)

Benallou, Abdelilah; El Alaoui El Abdallaoui, Habib; Garmes, Hocine

2018-02-01

The mechanism nature of the intramolecular Diels-Alder reaction has been performed; and thus, the changes of C-C bond forming/breaking along IRC are characterized in this study. Conceptual DFT analyses of the most favorable adduct fused/exo shows that the flux electronic will take place from diene to dienophile moiety. Moreover, ELF topological analysis based on the electron density predicts that C-C bond is formed by the coupling of two pseudoradical centers generated at the most significant atoms of the molecules. However, C2 vs C3, also C1 and C4 interaction comes mainly from the global electron density transfer which takes place along the reaction. Two- stage one-step is the proposed mechanism of this reaction, the first stage aims for the formation of C2-C3 σ bond while the second stage aims for C1-C4 σ bond formation. Interestingly, the observed asynchronicity of this IMDA reaction due principally to the asymmetric reorganization of electron density at the most attractive centers.

N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage.

Science.gov (United States)

Meng, Guangrong; Lalancette, Roger; Szostak, Roman; Szostak, Michal

2017-09-01

Despite recent progress in catalytic cross-coupling technologies, the direct activation of N-alkyl-N-aryl amides has been a challenging transformation. Here, we report the first Suzuki cross-coupling of N-methylamino pyrimidyl amides (MAPA) enabled by the controlled n N → π Ar conjugation and the resulting remodeling of the partial double bond character of the amide bond. The new mode of amide activation is suitable for generating acyl-metal intermediates from unactivated primary and secondary amides.

Study of the influence of the amount of PBI-H{sub 3}PO{sub 4} in the catalytic layer of a high temperature PEMFC

Energy Technology Data Exchange (ETDEWEB)

Lobato, Justo; Canizares, Pablo; Rodrigo, Manuel A.; Linares, Jose J.; Pinar, F. Javier [Chemical Engineering Department, Enrique Costa Building, University of Castilla-La Mancha, Av. Camilo Jose Cela, n 12, 13071, Ciudad Real (Spain)

2010-02-15

The influence of the amount of polybenzimidazole (PBI)-H{sub 3}PO{sub 4} (normalized with respect to the PBI loading, which expressed as C/PBI weight ratio) content in both the anode and cathode has been studied for a PBI-based high temperature proton exchange membrane (PEM) fuel cell. The electrodes prepared with different amounts of PBI have been characterized physically, by measuring the pore size distribution, and visualizing the surface microstructure. Afterwards, the electrochemical behaviour of the electrodes has been evaluated. The catalytic electrochemical activity has been measured by voltamperometry for each electrode prepared with a different PBI content, and the cell performance results have been studied, supported by the impedance spectra, in order to determine the influence of the PBI loading in each electrode. The best results have been achieved with a C/PBI weight ratio of 20, for both the anode and the cathode. A lower C/PBI weight ratio (larger amount of PBI in the catalytic layer) reduced the electrocatalytic activity, and impaired the mass transport processes, due to the large amount of polymer covering the catalyst particle, lowering the cell performance. A higher C/PBI weight ratio (lower amount of PBI in the catalytic layer) reduced the electrocatalytic activity, and slightly increased the ohmic resistance. The low amount of the polymeric ionic carrier PBI-H{sub 3}PO{sub 4} limited the proton mobility, despite of the presence of large amounts of ''free'' H{sub 3}PO{sub 4} in the catalytic layer. (author)

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

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Feriyanto Dafit

2017-01-01

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.

Exploration of the catalytic use of alkali metal bases

OpenAIRE

Bao, Wei

2017-01-01

This PhD thesis project was concerned with the use of alkali metal amide Brønsted bases and alkali metal alkoxide Lewis bases in (asymmetric) catalysis. The first chapter deals with formal allylic C(sp3)–H bond activation of aromatic and functionalized alkenes for subsequent C–C and C–H bond formations. The second chapter is focused on C(sp3)–Si bond activation of fluorinated pro-nucleophiles in view of C–C bond formations. In the first chapter, a screening of various metal amides...

Synthesis of heterocyclic compounds through palladium-catalyzed C-H cyclization processes.

Science.gov (United States)

Inamoto, Kiyofumi

2013-01-01

Herein, we describe our development of synthetic methods for heterocyclic compounds based on the palladium-catalyzed carbon-hydrogen bond (C-H) functionalization/intramolecular carbon-heteroatom (nitrogen or sulfur) bond formation process. By this C-H cyclization method, we efficiently prepared various N-heterocycles, including indazoles, indoles, and 2-quinolinones, as well as S-heterocycles such as benzothiazoles and benzo[b]thiophenes. Yields are typically good to high and good functional-group tolerance is observed for each process, thereby indicating that the method provides a novel, highly applicable synthetic route to the abovementioned biologically important heterocyclic frameworks. As an application of this approach, an auto-tandem-type, one-pot process involving the oxidative Heck reaction and subsequent C-H cyclization using cinnamamides and arylboronic acids as starting materials in the presence of a palladium catalyst was also developed for the rapid construction of the 2-quinolinone nucleus.

Microstructure in HIP-bonded F82H steel and its mechanical properties after irradiation

International Nuclear Information System (INIS)

Furuya, K.; Wakai, E.

2006-01-01

A first primary blanket structure is composed of the low-activation steel, e.g. F82H, and is fabricated by using a solid hot isostatic pressing (HIP) bonding method. A partial mock-up of such a blanket structure was successfully fabricated. The tensile specimen including HIP-bonded region possessed a sufficient strength and elongation under a non-irradiated condition as reported in our previous studies. In this study, the microstructures of HIP interface before irradiation were observed by a TEM, and the effects of irradiation on mechanical properties of the HIP-bonded region were also examined. TEM observation and elemental analysis of the HIP-bonded region before the irradiation were performed by using a FE-TEM of HF-2000 equipped with EDX spectroscopy. Tensile specimens (type SS-3) were prepared from a HIP-bonded region and a plate region of the mock-up block. Neutron irradiation was performed up to about 1.9 dpa at about 523 K in JMTR. After the irradiation, tensile test was performed at temperatures of 295 and 523 K. After the tensile test, OM observation at the rupture region and SEM observation at the fracture surface were conducted, respectively. TEM observation and analytical results revealed that the HIP interface possessed many precipitates, and enriched peak spectrum of chromium was detected from the precipitates. In addition, aspect of the spectrum was qualitatively equivalent to that of M23C6 in grain boundaries of F82H steel. In result, the HIP boundary has many M23C6 which were generally seen in grain boundaries of F82H steel, and it can be mentioned that the HIP interface is, in this sense, a new grain boundary. Obvious HIP boundary was seen at rupture region of tensile specimens sampled from the HIP-bonded region, by the macroscopic observation. It means that rupture do not occur in the HIP interface. In result, it can be mentioned that bondability of the HIP interfaces is kept under the irradiation and testing conditions. The strength and

Bonding effectiveness of self-etch adhesives to dentin after 24 h water storage.

Science.gov (United States)

Sarr, Mouhamed; Benoist, Fatou Leye; Bane, Khaly; Aidara, Adjaratou Wakha; Seck, Anta; Toure, Babacar

2018-01-01

This study evaluated the immediate bonding effectiveness of five self-etch adhesive systems bonded to dentin. The microtensile bond strength of five self-etch adhesives systems, including one two-step and four one-step self-etch adhesives to dentin, was measured. Human third molars had their superficial dentin surface exposed, after which a standardized smear layer was produced using a medium-grit diamond bur. The selected adhesives were applied according to their respective manufacturer's instructions for μTBS measurement after storage in water at 37°C for 24 h. The μTBS varied from 11.1 to 44.3 MPa; the highest bond strength was obtained with the two-step self-etch adhesive Clearfil SE Bond and the lowest with the one-step self-etch adhesive Adper Prompt L-Pop. Pretesting failures mainly occurring during sectioning with the slow-speed diamond saw were observed only with the one-step self-etch adhesive Adper Prompt L-Pop (4 out of 18). When bonded to dentin, the self-etch adhesives with simplified application procedures (one-step self-etch adhesives) still underperform as compared to the two-step self-etch adhesive Clearfil SE Bond.

(1)H, (13)C, (15)N backbone and side-chain resonance assignment of Nostoc sp. C139A variant of the heme-nitric oxide/oxygen binding (H-NOX) domain.

Science.gov (United States)

Alexandropoulos, Ioannis I; Argyriou, Aikaterini I; Marousis, Kostas D; Topouzis, Stavros; Papapetropoulos, Andreas; Spyroulias, Georgios A

2016-10-01

The H-NOX (Heme-nitric oxide/oxygen binding) domain is conserved across eukaryotes and bacteria. In human soluble guanylyl cyclase (sGC) the H-NOX domain functions as a sensor for the gaseous signaling agent nitric oxide (NO). sGC contains the heme-binding H-NOX domain at its N-terminus, which regulates the catalytic site contained within the C-terminal end of the enzyme catalyzing the conversion of GTP (guanosine 5'-triphosphate) to GMP (guanylyl monophosphate). Here, we present the backbone and side-chain assignments of the (1)H, (13)C and (15)N resonances of the 183-residue H-NOX domain from Nostoc sp. through solution NMR.

Improved catalytic properties of halohydrin dehalogenase by modification of the halide-binding site.

Science.gov (United States)

Tang, Lixia; Torres Pazmiño, Daniel E; Fraaije, Marco W; de Jong, René M; Dijkstra, Bauke W; Janssen, Dick B

2005-05-03

Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the dehalogenation of vicinal haloalcohols by an intramolecular substitution reaction, resulting in the formation of the corresponding epoxide, a halide ion, and a proton. Halide release is rate-limiting during the catalytic cycle of the conversion of (R)-p-nitro-2-bromo-1-phenylethanol by the enzyme. The recent elucidation of the X-ray structure of HheC showed that hydrogen bonds between the OH group of Tyr187 and between the Odelta1 atom of Asn176 and Nepsilon1 atom of Trp249 could play a role in stabilizing the conformation of the halide-binding site. The possibility that these hydrogen bonds are important for halide binding and release was studied using site-directed mutagenesis. Steady-state kinetic studies revealed that mutant Y187F, which has lost both hydrogen bonds, has a higher catalytic activity (k(cat)) with two of the three tested substrates compared to the wild-type enzyme. Mutant W249F also shows an enhanced k(cat) value with these two substrates, as well as a remarkable increase in enantiopreference for (R)-p-nitro-2-bromo-1-phenylethanol. In case of a mutation at position 176 (N176A and N176D), a 1000-fold lower catalytic efficiency (k(cat)/K(m)) was obtained, which is mainly due to an increase of the K(m) value of the enzyme. Pre-steady-state kinetic studies showed that a burst of product formation precedes the steady state, indicating that halide release is still rate-limiting for mutants Y187F and W249F. Stopped-flow fluorescence experiments revealed that the rate of halide release is 5.6-fold higher for the Y187F mutant than for the wild-type enzyme and even higher for the W249F enzyme. Taken together, these results show that the disruption of two hydrogen bonds around the halide-binding site increases the rate of halide release and can enhance the overall catalytic activity of HheC.

The electronic donation and frequency shifts on the YCCH⋯BH4- boron-bonded complexes (Y = H, CH3, CF3 and CCl3)

Science.gov (United States)

Pordeus, Renato Q.; Rego, Danilo G.; Oliveira, Boaz G.

2015-06-01

In this theoretical work, the tetrahydroborate ion (BH4-) was used as proton acceptor in the formation of the YCC-H⋯BH4- complexes (Y = H, CH3, CCl3 and CF3). Using B3LYP/6-311++G(d,p) level of theory, the results of structure corroborate with the analyses of infrared spectra showing that the changes in the bond lengths are in good agreement with the frequency shifts of the HCC-H, H3CCC-H, Cl3CCC-H and F3CCC-H proton donors. Based on the calculations carried out by the Quantum Theory of Atoms in Molecules (QTAIM), the reductions of electronic density corroborate with the red shifts in the frequencies of the C-H bonds. In addition to that, the C-H bonds are polarized because the contributions of s orbital diminish whereas of p increase. In line with this, the variations on the atomic radii computed via QTAIM calculations show that carbon outweigh hydrogen as follows (ΔrC > ΔrH). This scenario is indirectly supported by the Bent's rule of the chemical bonding. Although the interaction energies (corrected with BSSE and ZPE) vary between -19 and -67 kJ mol-1, these complexes interact without covalent character.

Atropisomerism about Aryl-C(sp(3)) Bonds: Conformational Behavior of Substituted Phenylcyclohexanes in Solution.

Science.gov (United States)

Flos, Manon; Lameiras, Pedro; Denhez, Clément; Mirand, Catherine; Berber, Hatice

2016-03-18

A catalytic hydrogenation of cannabidiol derivatives known as phenylcyclohexenes was used to prepare epimeric (1R,1S) and/or rotameric (M,P) phenylcyclohexanes. The reaction is diastereoselective, in favor of the 1S epimer, when large groups are attached to the phenyl ring. For each epimer, variable-temperature NMR experiments, including EXSY spectroscopy and DFT calculations, were used to determine the activation energies of the conformational exchange arising from the restricted rotation about the aryl-C(sp(3)) bond that led to two unequally populated rotamers. The conformational preference arises essentially from steric interactions between substituents vicinal to the pivot bond. The conformers of epimers (1S)-2e,f show high rotational barriers of up to 92 kJ mol(-1), unlike those of (1R)-2e,f and with much lower barriers of ∼72 kJ mol(-1). The height of the barriers not only depends on the substituents at the axis of chirality but also is influenced by the position of a methyl group on the monoterpene ring. The feature most favorable to high rotational barriers is when the methyl at C1 lies equatorially. This additional substituent effect, highlighted for the first time, seems fundamental to allowing atropisomerism in hindered ortho-substituted phenylcyclohexanes.

The decomposition of mixed oxide Ag2Cu2O3: Structural features and the catalytic properties in CO and C2H4 oxidation

Science.gov (United States)

Svintsitskiy, Dmitry A.; Kardash, Tatyana Yu.; Slavinskaya, Elena M.; Stonkus, Olga A.; Koscheev, Sergei V.; Boronin, Andrei I.

2018-01-01

The mixed silver-copper oxide Ag2Cu2O3 with a paramelaconite crystal structure is a promising material for catalytic applications. The as-prepared sample of Ag2Cu2O3 consisted of brick-like particles extended along the [001] direction. A combination of physicochemical techniques such as TEM, XPS and XRD was applied to investigate the structural features of this mixed silver-copper oxide. The thermal stability of Ag2Cu2O3 was investigated using in situ XRD under different reaction conditions, including a catalytic CO + O2 mixture. The first step of Ag2Cu2O3 decomposition was accompanied by the appearance of ensembles consisting of silver nanoparticles with sizes of 5-15 nm. Silver nanoparticles were strongly oriented to each other and to the surface of the initial Ag2Cu2O3 bricks. Based on the XRD data, it was shown that the release of silver occurred along the a and b axes of the paramelaconite structure. Partial decomposition of Ag2Cu2O3 accompanied by the formation of silver nanoparticles was observed during prolonged air storage under ambient conditions. The high reactivity is discussed as a reason for spontaneous decomposition during Ag2Cu2O3 storage. The full decomposition of the mixed oxide into metallic silver and copper (II) oxide took place at temperatures higher than 300 °C regardless of the nature of the reaction medium (helium, air, CO + O2). Catalytic properties of partially and fully decomposed samples of mixed silver-copper oxide were measured in low-temperature CO oxidation and C2H4 epoxidation reactions.

Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds

Directory of Open Access Journals (Sweden)

Ibon Alkorta

2017-10-01

Full Text Available It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N2, CO, HC≡CH, CH2=CH2, C3H6, PH3, H2S, HCN, H2O, H2CO and NH3 and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H2O, F2, Cl2, Br2, ClF, BrCl, H3SiF, H3GeF, F2CO, CO2, N2O, NO2F, PH2F, AsH2F, SO2, SeO2, SF2, and SeF2 can be represented to good approximation by means of the equation D e = c ′ N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ′ is a constant, conveniently chosen to have the value 1.00 kJ mol−1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1 the hydrogen bond; (2 the halogen bond; (3 the tetrel bond; (4 the pnictogen bond; and (5 the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

Neutron Crystallography for the Study of Hydrogen Bonds in Macromolecules

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Esko Oksanen

2017-04-01

Full Text Available Abstract: The hydrogen bond (H bond is one of the most important interactions that form the foundation of secondary and tertiary protein structure. Beyond holding protein structures together, H bonds are also intimately involved in solvent coordination, ligand binding, and enzyme catalysis. The H bond by definition involves the light atom, H, and it is very difficult to study directly, especially with X-ray crystallographic techniques, due to the poor scattering power of H atoms. Neutron protein crystallography provides a powerful, complementary tool that can give unambiguous information to structural biologists on solvent organization and coordination, the electrostatics of ligand binding, the protonation states of amino acid side chains and catalytic water species. The method is complementary to X-ray crystallography and the dynamic data obtainable with NMR spectroscopy. Also, as it gives explicit H atom positions, it can be very valuable to computational chemistry where exact knowledge of protonation and solvent orientation can make a large difference in modeling. This article gives general information about neutron crystallography and shows specific examples of how the method has contributed to structural biology, structure-based drug design; and the understanding of fundamental questions of reaction mechanisms.

Supramolecular Recognition Allows Remote, Site-Selective C-H Oxidation of Methylenic Sites in Linear Amines.

Science.gov (United States)

Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel

2017-12-18

Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp 3 )-H hydroxylation with H 2 O 2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C-H bonds, no matter the chain length. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroelectrochemical Study of Carbon Monoxide and Ethanol Oxidation on Pt/C, PtSn(3:1/C and PtSn(1:1/C Catalysts

Directory of Open Access Journals (Sweden)

Rubén Rizo

2016-09-01