Reactions of the anionic gallium(I) heterocycle salt, [K(tmeda)][Ga(DAB)] (DAB = N(Dip)C(H) (2); Dip - C6H3Pr2i-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 NBut)] and [(IPr)Cu kappa(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.