Me3Ga was allowed to react with a series of ten amines at 110°C in toluene to give 75 to 90% yields of the corresponding aminogallanes, [Me2GaR]2 [R = NMe2, NEt2, NPrn2, NBun2, NBui2, N(c-C6H11)2, NC4H8, NC5H10, NC6H12, and N(CH2CH2)2NMe], via a 1,2-elimination of CH4. Similarly, [Me2 A1NBus2]2 and [Me2A1N(c-C6H11)2]2 were prepared by an analogous thermolysis reaction. On the other hand, synthesis of [Me2GaNPri2]2, [Me2GaNBus2]2, and [Me2GaN(CH2Ph)2]2 was achieved by the reaction of Me2GaCl with the respective lithium amide. A comparison of the 1H and 13C NMR chemical shifts for the aminogallanes with those previously obtained for the analogous series of aminoalanes indicates a similar sensitivity to the influence of the amide moiety. X-ray crystal structures were determined for [Me2GaN(CH2Ph)2]2, which has a slightly puckered four-membered Ga2N2 core, and [Me2GaN(CH2CH2)2NMe]2, which has a planar four-membered Ga2N2 core. © 1997 Elsevier Science S.A.