Transition metal chemistry of low valent group 13 organyls

The coordination of low-valent group 13 organyls (ER)-R-1 [E = At, G a, 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 (ER)-R-1 moiety is formally isolobal with CO and PR3 (R = alkyl, Cp*) or carbenes (R = chelating group) with varying sigma-donor and pi-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 (ER)-R-1 into transition metal halide bonds are described. Furthermore, the reactivity of homoleptic complexes M-a((ER)-R-1)(b) is discussed, outlining the use of these new complex types in bond activation reactions. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.