Methane Activation by Os(II) Complexes: Theoretical Study of Methane Oxidative Addition to Isomeric OsCl2(PH3)2 Complexes by RHF, MP2, and DFT Methods Full article
| Journal |
Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210 |
||
|---|---|---|---|
| Output data | Year: 1998, Volume: 39, Number: 4, Pages: 476-484 Pages count : 9 | ||
| Tags | C-H BOND; TRANSITION-METAL ATOMS; MOLECULAR CALCULATIONS; REDUCTIVE ELIMINATION; GAS-PHASE; ENERGY; ALKANES; IR; MECHANISMS; IRIDIUM | ||
| Authors |
|
||
| Affiliations |
|
Abstract:
The oxidative addition of methane to a model Os(Cl)(2)(PH3)(2) complex was theoretically studied using restricted Hartree-Fock (RHF) calculations refined by taking into account electron energy correlation by the MP2 and DFT methods. The calculation predicts the existence of a number of stable isomers of Os(Cl)(2)(PH3)(2). Quantum chemical analysis of methane reactions with three isomers suggests the formation of sigma-complexes (eta(2)-CH4)Os(Cl)(2)(PH3)(2) for some isomers. The pathways of the oxidative addition reaction to three isomers were calculated. The initial tetrahedral isomer forms the most stable sigma-complex with methane, although it is incapable of activating a C-H bond. Only square-pyramidal isomer activates methane by oxidative addition with low activation energy and yields a methylosmium hydride product.
Cite:
Avdeev V.I.
, Zhidomirov G.M.
Methane Activation by Os(II) Complexes: Theoretical Study of Methane Oxidative Addition to Isomeric OsCl2(PH3)2 Complexes by RHF, MP2, and DFT Methods
Kinetics and Catalysis. 1998. V.39. N4. P.476-484. WOS Scopus РИНЦ ANCAN
Methane Activation by Os(II) Complexes: Theoretical Study of Methane Oxidative Addition to Isomeric OsCl2(PH3)2 Complexes by RHF, MP2, and DFT Methods
Kinetics and Catalysis. 1998. V.39. N4. P.476-484. WOS Scopus РИНЦ ANCAN
Original:
Авдеев В.И.
, Жидомиров Г.М.
Активация метана комплексами Os(II): теоретический анализ окислительного присоединения метана к изомерам комплекса OsCl2(PH3)2 методами RHF, MP2 и DFT
Кинетика и катализ. 1998. Т.39. №4. С.513-522. РИНЦ publication_identifier_short.rz_viniti_identifier_type
Активация метана комплексами Os(II): теоретический анализ окислительного присоединения метана к изомерам комплекса OsCl2(PH3)2 методами RHF, MP2 и DFT
Кинетика и катализ. 1998. Т.39. №4. С.513-522. РИНЦ publication_identifier_short.rz_viniti_identifier_type
Dates:
| Submitted: | Jun 10, 1997 |
| Published print: | Jul 1, 1998 |
Identifiers:
| Web of science: | WOS:000076157100007 |
| Scopus: | 2-s2.0-0005299736 |
| Elibrary: | 13284872 |
| Chemical Abstracts: | 1998:653464 |
| Chemical Abstracts (print): | 129:330859 |