Transition Metal Chemistry of Low Valent Group 13 Organyls

Abstract The coordination of low‐valent group 13 organyls EIR [E = Al, Ga, In; R = Cp*, C(SiMe3)3] to transition metals has attracted increasing interest over the past decade. Complexes and cluster compounds of these new ligands with a number of transition metals have been isolated and characterised. The EIR moiety is formally isolobal with CO and PR3 (R = alkyl, Cp*) or carbenes (R = chelating group) with varying σ‐donor and π‐acceptor properties depending on the organic group R as well as the group 13 metal E. In this review, different ways of forming M−E bonds such as substitution reactions of labile ligands or insertion of EIR into transition metal halide bonds are described. Furthermore, the reactivity of homoleptic complexes Ma(EIR)b is discussed, outlining the use of these new complex types in bond activation reactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)