Bonding in metal hexacarbonyls

Ramiro Arratia-Perez, Cary Y. Yang

Resultado de la investigación: Article

31 Citas (Scopus)

Resumen

A detailed analysis of the valence molecular orbitals (MO) in Cr(CO) 6, Mo(CO)6, and W(CO)6 is presented. A generalized bonding scheme, which includes participation of metal p electrons in the metal-ligand bond, emerges from our results. The metal p electrons are also responsible for effecting mixings between different sets of carbonyl 5σ and 1π orbitals. In these hexacarbonyls, this "σ" + "π" metal-ligand bonding contribution is quantitatively as significant as the well known σ donation and π-back-donation components. The MO's obtained with the Dirac scattered-wave (DSW) method are also used to determine the importance of relativistic effects in this series. The DSW results show that even in W(CO)6, relativistic effects are qualitatively unimportant. Extensive comparisons with existing theoretical and experimental data are made for both ground-state and transition-state calculations.

Idioma originalEnglish
Páginas (desde-hasta)4005-4014
Número de páginas10
PublicaciónThe Journal of Chemical Physics
Volumen83
N.º8
EstadoPublished - 1985

Huella dactilar

Metals
relativistic effects
metals
Ligands
ligands
Electrons
Molecular orbitals
Electron transitions
Ground state
molecular orbitals
electrons
valence
orbitals
ground state
hexacarbonyltungsten

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Citar esto

Arratia-Perez, Ramiro ; Yang, Cary Y. / Bonding in metal hexacarbonyls. En: The Journal of Chemical Physics. 1985 ; Vol. 83, N.º 8. pp. 4005-4014.
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Arratia-Perez, R & Yang, CY 1985, 'Bonding in metal hexacarbonyls', The Journal of Chemical Physics, vol. 83, n.º 8, pp. 4005-4014.

Bonding in metal hexacarbonyls. / Arratia-Perez, Ramiro; Yang, Cary Y.

En: The Journal of Chemical Physics, Vol. 83, N.º 8, 1985, p. 4005-4014.

Resultado de la investigación: Article

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T1 - Bonding in metal hexacarbonyls

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AU - Yang, Cary Y.

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N2 - A detailed analysis of the valence molecular orbitals (MO) in Cr(CO) 6, Mo(CO)6, and W(CO)6 is presented. A generalized bonding scheme, which includes participation of metal p electrons in the metal-ligand bond, emerges from our results. The metal p electrons are also responsible for effecting mixings between different sets of carbonyl 5σ and 1π orbitals. In these hexacarbonyls, this "σ" + "π" metal-ligand bonding contribution is quantitatively as significant as the well known σ donation and π-back-donation components. The MO's obtained with the Dirac scattered-wave (DSW) method are also used to determine the importance of relativistic effects in this series. The DSW results show that even in W(CO)6, relativistic effects are qualitatively unimportant. Extensive comparisons with existing theoretical and experimental data are made for both ground-state and transition-state calculations.

AB - A detailed analysis of the valence molecular orbitals (MO) in Cr(CO) 6, Mo(CO)6, and W(CO)6 is presented. A generalized bonding scheme, which includes participation of metal p electrons in the metal-ligand bond, emerges from our results. The metal p electrons are also responsible for effecting mixings between different sets of carbonyl 5σ and 1π orbitals. In these hexacarbonyls, this "σ" + "π" metal-ligand bonding contribution is quantitatively as significant as the well known σ donation and π-back-donation components. The MO's obtained with the Dirac scattered-wave (DSW) method are also used to determine the importance of relativistic effects in this series. The DSW results show that even in W(CO)6, relativistic effects are qualitatively unimportant. Extensive comparisons with existing theoretical and experimental data are made for both ground-state and transition-state calculations.

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