Giant cluster catalysis: possible intermediacy of nitrene and carbene species

Моисеев, И. И.; Stromnova, T. A.; Варгафтик, М. Н.; Orlova, S. T.; Chernysheva, T. V.; Stolarov, Igor P.

doi:10.1016/s0920-5861(99)00043-7

Cited by 29 publications

(19 citation statements)

References 18 publications

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“…The copper-containing portion (L′Cu, where L′ is the parent -diketiminate anion, C 3 N 2 H 5 -) of the nitrene models is formally a closed-shell d 10 Cu I ion, and hence a singlet ground state is expected for L′Cu (a supposition supported by DFT calculations). For PhN, a singlet ( 1 A 2 )/triplet ( 3 A 2 ) splitting of ∼18 kcal/mol is derived from a combination of multiconfiguration calculations and experiment.…”

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confidence: 92%

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Bonding and Structure of Copper Nitrenes

2008

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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 ( -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.

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confidence: 92%

“…10 Liu et al discuss the formation of ArNCO from alkyl-nitro complexes by a copper zeolite catalyst. 11 Kober et al report the formation of halogenated ArNCO from halogenated nitroaromatics using a catalyst that is 5% PdCl 2 and 5% CuCl 2 supported on SiC.…”

Section: Introductionmentioning

confidence: 99%

Bonding and Structure of Copper Nitrenes

2008

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“…Moreover, the difficulties in transport and storage of H 2 gas lead to additional cost to the production of aniline. Alternatively, nitroarene compounds can be reduced to aromatic amines by “extracting” hydrogen from hydrogen‐donor molecules, that is, transfer hydrogenation 14–20. Among the available hydrogen donors,21–23 FA, which may be derived from biomass with low toxicity and high stability, is an abundant and cheap hydrogen source for safe hydrogen usage and storage 24–26.…”

Section: Introductionmentioning

confidence: 99%

Photochemically Engineering the Metal–Semiconductor Interface for Room‐Temperature Transfer Hydrogenation of Nitroarenes with Formic Acid

Cai

Gong

et al. 2014

Chemistry A European J

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A mild photochemical approach was applied to construct highly coupled metal-semiconductor dyads, which were found to efficiently facilitate the hydrogenation of nitrobenzene. Aniline was produced in excellent yield (>99 %, TOF: 1183) using formic acid as hydrogen source and water as solvent at room temperature. This general and green catalytic process is applicable to a wide range of nitroarenes without the involvement of high-pressure gases or sacrificial additives.

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“…Catalytic activity in the reaction was found for rhodium [1][2][3], ruthenium [4][5][6], palladium [7][8][9][10] and selenium [11][12][13] compounds. The palladium catalysts, on account of their relatively lower price and a high activity and selectivity, arouse greater interest.…”

Section: Introductionmentioning

confidence: 99%