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Analysis of σ-Bonding, π-(Foack)Bonding and the Synergic Effect in Cr(CO)6. Comparison of Hartree-Fock and Xα Results for Metal-CO Bonding

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Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry

Part of the book series: NATO ASI Series ((ASIC,volume 176))

Abstract

LCAO-Xα calculations with large STO basis sets are used to establish the relative contributions of σ-bonding, π-(back)bonding and notably the synergic effect to the total metal-CO bond strength in Cr(CO)6. It appears that the π-bond is about twice as strong as the σ-bond. The synergic effect makes a contribution of the same order of magnitude as the π- and σ-bonds. The Cr-C and C-O bond distances are optimized, and the Alg vibration frequencies are calculated and compared to both Hartree-Fock calculations and experiment. Contrary to the Hartree-Fock model, which gives generally too low metal-ligand bond energies and too long bonds, the Xα model leads to too large metal-ligand bond energies, too short bond lengths and too high metal-CO vibration energies. The reduction of the C-O stretch frequency upon coordination is calculated very accurately.

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Author information

Authors and Affiliations

  1. Chemistry Department, Vrije Universiteit, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands

    E. J. Baerends & A. Rozendaal

Authors
  1. E. J. Baerends
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  2. A. Rozendaal
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Editors and Affiliations

  1. Centre National de la Recherche Scientifique, Strasbourg, France

    A. Veillard

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© 1986 D. Reidel Publishing Company

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Baerends, E.J., Rozendaal, A. (1986). Analysis of σ-Bonding, π-(Foack)Bonding and the Synergic Effect in Cr(CO)6. Comparison of Hartree-Fock and Xα Results for Metal-CO Bonding. In: Veillard, A. (eds) Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry. NATO ASI Series, vol 176. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4656-9_12

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  • DOI: https://doi.org/10.1007/978-94-009-4656-9_12

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-90-277-2237-9

  • Online ISBN: 978-94-009-4656-9

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