The reactivity of olefin containing complexes of the d(8) metals Ru-0 and Rh-1 toward GaCp* and AlCp* is presented. [Ru(eta(4)-butadiene)(PPh3)(3)] reacts with GaCp* to give the substitution product [Ru(eta(4)-butadiene)(PPh3)(2)(GaCp*)] (1), which proved to be stable in the presence of GaCp* even under hydrogenolytic conditions. In contrast, the bis-styrene complex [Ru(PPh3)(2)(styrene)(2)] undergoes full substitution of the olefin ligands to give [Ru(PPh3)(2)(GaCp*)(3)] (2), whereas reaction of [Ru(eta(2),eta(2)-COD)(eta(6)-COT)] (COD = 1,5-cyclooctadiene, C8H12, COT = 1,3,5-cyclooctatriene, C8H10) and GaCp* leads to [Ru(eta(2),eta(2)-COD)(GaCp*)(3)] (3) under mild hydrogenolytic conditions. Analogously, the Rh-I compounds [{Rh(eta(2),eta(2)-NBD)(PCy3)(2)}{BArF}] (NBD = norbomadiene) and [{Rh(eta(2),eta(2)-COD)(2)}{BArF}]({BArF}=B{[C6H3(CF3)(2)](4)}) yield the complexes [{Rh(eta(2),eta(2)-NBD)(PCy3)(GaCp*)(2)}{BArF}] (4), [{Rh(eta(2),eta(2)-COD)(GaCp*)(3)}{BArF}] (5), and [{Rh(eta(2),eta(2)-COD)(AlCp*)(3)}{BArF}] (6) upon reaction with the appropriate ECp* ligand (E = Al, Ga). All new complexes have been characterized by means of H-1 and C-13 NMR spectroscopy and elemental analysis, as well as X-ray single crystal structure analysis in the case of 1-5.