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Electronic Spectroscopy of Metal-Metal σ-Symmetry Interactions

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Understanding Molecular Properties

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Abstract

The electronic spectra of d7-d7 metal-metal-bonded compounds are dominated by σ→σ* transitions, where the lowest energy transition is either metal-metal (dσ→dσ*) or axial-ligand charge transfer (L(σ)→dσ*); the relative energetics are determined mainly by metal-metal bond strength and axial-ligand reducing character. In some cases, both σ→σ* transitions are observed. Relatively weak electronic absorption bands are attributable to dπ→dσ*(M2) and dπ→dσ*(M-Leq), where the ligand-field strength of the equatorial ligand controls the relative excitation energies. The equatorial ligands also affect the strength of the metal-metal bond, and the L(σ)→dσ* transition is shown to be strongly responsive to this perturbation. If the lowest energy σ→σ* transition is L(σ)→dσ*, however, its energy need not correlate with the metal-metal bond length. The electronic spectra of mixed-valence (e.g., d7-d8) and longer-chain metal-metal-bonded compounds can be interpreted in terms of the molecular orbital levels developed for d7-d7 species.

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Authors and Affiliations

  1. Arthur Amos Noyes Laboratory, California Institute of Technology, Pasadena, California, 91125, USA

    Vincent M. Miskowski & Harry B. Gray

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  1. Vincent M. Miskowski
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  2. Harry B. Gray
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Editors and Affiliations

  1. Department of Physical Chemistry, University of Copenhagen, Denmark

    John Avery  & Aage E. Hansen  & 

  2. Department of Physical Chemistry, The Technical University of Denmark, Lyngby, Denmark

    Jens Peder Dahl

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© 1987 D. Reidel Publishing Company

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Miskowski, V.M., Gray, H.B. (1987). Electronic Spectroscopy of Metal-Metal σ-Symmetry Interactions. In: Avery, J., Dahl, J.P., Hansen, A.E. (eds) Understanding Molecular Properties. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-3781-9_1

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  • DOI: https://doi.org/10.1007/978-94-009-3781-9_1

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-8182-5

  • Online ISBN: 978-94-009-3781-9

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