Reactions of the anionic gallium(I) heterocycle salt, [K(tmeda)][Ga(DAB)] (DAB = {N(Dip)C(H)} 2; Dip = C 6H 3Pr i 2-2,6), with a series of groups 6–9 and 11 metal halide complexes have given rise to the metal gallyl complexes, [CpCr(IMes){Ga(DAB)}] (IMes = :C{(Mes)NC(H)} 2; Mes = mesityl), [M(tmeda){Ga(DAB)} 2] (M = Mn, Fe or Co) and [Cu(dppe){Ga(DAB)}] (dppe = 1,2-bis(diphenylphosphino)ethane). The majority of the complexes have been crystallographically characterized. The reactivity of the previously reported copper(I) gallyl complex, [(IPr)Cu{Ga(DAB)}] (IPr = :C{(Dip)NC(H)} 2), towards a variety of unsaturated substrates has been explored. Three crystallographically characterized complexes have arisen from this phase of the study, viz. [(IPr)CuC CPh], [(IPr)Cu{Ga(DAB)}(C NBu t)] and [(IPr)Cu{κ 1-OC(O)C( CNHDip)(NHDip)}]. The results of these investigations show that the reactivity of [(IPr)Cu{Ga(DAB)}] is significantly different to that of related copper boryl complexes.