Synthesis, Structures, and Reactivity of Organostannanides and Organogermanides of Copper(I)

Organogermane and organostannane compounds are valuable reagents in cross coupling reactions, and copper(I) germanide and stannanide complexes can provide convenient access to these compounds. This review presents the chemistry of copper(I) germanide and stannanide complexes, with a particular focus on systems at the frontier of organic and inorganic chemistry where structural characterisation of coordination complexes facilitates rationalisation of organic mechanisms. These species show both similarities to, and significant divergences from their lighter silanide congeners. For example, they are all viable sources of the relevant organotetranide anion, but in the cases of both germanium and tin, the tetranides can be accessed via direct deprotonation of the corresponding tetranes, a reaction unknown for silicon. Further divergences between copper(I) germanides and stannanides are highlighted; whilst both can be used in productive organic transformations to access organotetranes, catalytic reactions are only reported for germanium. The rather striking ability of triphenlstannides to acts as sources of the phenyl anion are discussed; the mechanism of this reaction is still subject to discussion, but its absence in the chemistry of germanium and silicon is now well‐rationalised. We conclude this review by considering potential research directions in the synthesis and exploitation of copper(I) germanides and stannanides.