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Keywords:

  • Solid-state reactions;
  • Cluster compounds;
  • Metal–metal interactions

Abstract

Metals in low oxidation states are capable of forming metal–metal bonds. An attempt has been made to classify the numerous phases and structures occurring in such metal-rich systems of valence electron poor metals in some sort of order from a rather general point of view. With this purpose in mind, clusters of these elements, their different types of interconnections, and their condensation via shared metal atoms, which finally leads to extended M[BOND]M bonded structures, are described. Interstitial atoms play an important role in stabilizing electron deficient clusters, and can actually lead to the loss of all M[BOND]M bonds. Surprising similarities emerge between apparently very different systems as the metal-rich oxides of alkali metals, the oxides, halides, and chalcogenides of d transition metals, and the halides and carbide halides of the lanthanoids.