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Metal-metal interactions in transition metal clusters with π-donor ligands

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Structural and Electronic Paradigms in Cluster Chemistry

Part of the book series: Structure and Bonding ((STRUCTURE,volume 87))

Abstract

A variety of structural types of transition metal clusters containing mainly π-donor ligands are reviewed. Their structure and bonding are analyzed using a simple and unified molecular orbital approach based on the consideration of metal-metal bonding as arising from the interaction of the frontier orbitals of individual metal fragments derived from their local MLn coordination. This kind of “local metal frontier orbital” approach allows us to construct metal-metal orbital interaction diagrams in a convenient way. Using these molecular orbital diagrams, relevant optimal electron counts for major structural types are discussed. It is emphasized that the “t2g” set fragment orbitals, which are non-bonding in carbonyl clusters, play the crucial role in metal-metal bonding for clusters with π-donor ligands. Bonding characteristics for Mo(W)-Fe-S, Ni-S(Se) and related clusters are also discussed.

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  1. Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong

    Zhenyang Lin & Man-Fai Fan

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D. M. P. Mingos

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Lin, Z., Fan, MF. (1997). Metal-metal interactions in transition metal clusters with π-donor ligands. In: Mingos, D.M.P. (eds) Structural and Electronic Paradigms in Cluster Chemistry. Structure and Bonding, vol 87. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0018030

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