The reactions of molybdenum(0) and rhodium(I) olefin containing starting materials with the carbenoid group 13 metal ligator ligand GaR (R = Cp*, DDP; Cp* = pentamethylcyclopentadienyl, DDP = HC(CMeNC6H3-2,6-Pr-i(2))(2)) were investigated and compared. Treatment of [Mo(eta(4)-butadiene)(3)] with GaCp* under hydrogen atmosphere at 100 degrees C yields the homoleptic, hexa coordinated, and sterically crowded complex [Mo(GaCp*)(6)] (1) in good yields >= 50%. Compound 1 exhibits an unusual and high coordinated octahedral [MoGa6] core. Similarly, [Rh(GaCp*)s][CF3SO3] (2) and [Rh(GaCp*)(5)][BArF] (3) (BArF = B{C6H3(CF3)(2)}(4)) are prepared by the reaction of GaCp* with the rhodium(I) compound [Rh(coe)(2)(CF3SO3)](2) (coe = cydooctene) and subsequent anion exchange in case of 3. Compound 2 features a trigonal bipyramidal [RhGa5] unit. In contrast, reaction of excess Ga(DDP) with [Rh(coe)(2)(CF3SO3)](2) does not result in a high coordinated homoleptic complex but instead yields [(coe)(toluene)Rh{Ga(DDP)}(CF3SO3)] (4). The common feature of 2 and 4 in the solid state structure is the presence of short CF3SO2O center dot center dot center dot Ga contacts involving the GaCp* or rather the Ga(DDP) ligand. Compounds 1, 2, and 4 have been fully characterized by single crystal X-ray diffraction, variable temperature H-1 and C-13 NMR spectroscopy, IR spectroscopy, mass spectrometry, as well as elemental analysis.