Me2AlH and Bui2AlH were reacted with a series of nine aminoarsines, Me2AsR (R = NMe2, NPrn2, NPri2, NBun2, NBui2, NC4H8, NC5H10, NC6H12, and N(C2H4)2NMe), in C6D6 at room temperature, and the reactions were monitored by 1H and 13C NMR spectroscopy. The relative rates for initial As-N bond cleavage and final product formation were dependent on the steric requirements of the alkyl groups attached to aluminum and nitrogen in the starting materials. Overall rates were slower with Bui2AlH than with Me2AlH for a given aminoarsine. For most of the reactions, the predominant Al-containing products were the dimeric aminoalane compounds, [Me2AlR]2 and [Bui2AlR]2. Although Al-N bond formation was the prefered mode of reaction, Al-As bond formation was also observed when the bulky Pri and Bui aminoarsine derivatives were used. The [Bui2AlR]2 compounds were synthesized independently by the reaction of Bui2AlH and the respective amine or, in the case of [Bui2-AlNBui2]2, by the reaction of Bui2AlCl and LiNBui2 X-ray crystal structures were determined for the compounds [Me2AlNC6H12]2, [Me2AlN(C2H4)2NMe]2, [Bui2AlNMe2]2, and [Bui2AlN-(C2H4)2NMe] 2. All of the compounds have planar Al2N2 rings with the exception of [Bui2-AlN(C2H4)2NMe] 2, which displays a puckered Al2N2 ring.