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Structural and Bonding Principles in Metal Halide Cluster Chemistry

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Modern Perspectives in Inorganic Crystal Chemistry

Part of the book series: NATO ASI Series ((ASIC,volume 382))

Abstract

Metal cluster halides M6X12 and M’6X8 and their alkali metal derivatives exhibit a variety of structure types because of the evident need to bond terminal or shared halide at all metal vertices. The versatility of systems with group 3 and 4 transition metals is greatly increased by the presence of interstitial heteroatoms (Z) within all thermodynamically stable clusters. The 24 examples of Z provide a wide range of valence electrons and include many that are themselves metals. Structural and bonding principles are described, including the novel characteristics of some cation sites, the regular effects that cations have on cluster bond distances, matrix effects that arise because of characteristic X⋯X or M - X distances and their influence on metal - metal bonding and electronic configurations, and the use of metal - metal bond orders to characterize matrix effects. The condensation products of octahedral clusters, particularly chains centered by heterometals and double-metal sheet products, are also noted.

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  1. Department of Chemistry, Iowa State University, Ames, Iowa, 50011, USA

    John D. Corbett

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  1. John D. Corbett
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  1. Laboratoire de Cristallographie aux Rayons X, University of Geneva, Geneva, Switzerland

    Erwin Parthé

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Corbett, J.D. (1992). Structural and Bonding Principles in Metal Halide Cluster Chemistry. In: Parthé, E. (eds) Modern Perspectives in Inorganic Crystal Chemistry. NATO ASI Series, vol 382. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-2726-4_3

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  • DOI: https://doi.org/10.1007/978-94-011-2726-4_3

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