Heterolytic activation of C?H bond in methane with (HN?CHCH?NH)M(CH3) (M = Pd+, Pt+, Rh+, Ir+, Rh, Ir): Comparative density functional study of activation mechanisms
| Autor: | Ole Swang, Hanne Heiberg, Odd Gropen |
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| Rok vydání: | 2003 |
| Předmět: |
Chemistry
Cationic polymerization Condensed Matter Physics Photochemistry Metathesis Medicinal chemistry Heterolysis Oxidative addition Atomic and Molecular Physics and Optics Methane Metal chemistry.chemical_compound visual_art Arenium ion visual_art.visual_art_medium Density functional theory Physical and Theoretical Chemistry |
| Zdroj: | International Journal of Quantum Chemistry. 92:391-399 |
| ISSN: | 1097-461X 0020-7608 |
| DOI: | 10.1002/qua.10525 |
| Popis: | Activation of methane by oxidative addition and σ-bond metathesis has been investigated for (N-N)M(CH3) (M = Pd+, Pt+, Rh+, Ir+, Rh, Ir; N-N = (HNCHCHNH) using different density functional approaches. The pathway of oxidative addition is in general favored, the exceptions being Pd+ and Rh+. Oxidative addition is clearly more favorable for the third-row metal complexes than those of the second row. The third-row metal complexes also tend to have a lower activation barrier for σ-bond metathesis than those of the second row. In each case, the oxidative addition is preceded by formation of a sigma complex. The bonding energies of these complexes are significantly stronger for the cationic systems. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 |
| Databáze: | OpenAIRE |
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