Abstract

This chapter discusses clusters that contain higher oxidation state metals from the early to mid d-block metals with π-donor ligands, focusing on metal halide clusters and their derivatives. It considers three cluster cores or metal centres in a closed framework: triangle, square-based pyramid, and octahedron. It cites an example of a semi-interstitial atom that is partially surrounded by metal centres and is rather exposed. The chapter describes the structural features common to niobium and tantalum halide clusters. These generally consist of an octahedral metal core supported by edge-bridging and terminal ligands. It reviews the crucial role of an interstitial atom as it provides valence electrons for the stabilization of an electron-poor compound from within the cage without imposing steric demands among the ligands around the outside of the cage.

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