The reactions of (Me2AlH)3 with Me2AsNMe2, MeAs(NMe2)2, and As(NMe2)3 were investigated as a function of time at room temperature and over the temperature range -90 to 24°C by use of 1H and 13C NMR spectroscopy. (Me2AlH)3 was found to be very reactive toward the aminoarsines, even at -90°C, and no stable Me2AlH-aminoarsine adducts were observed. Instead, the initial stages of the reactions involved ASN bond cleavage with the generation of highly reactive AlN- and AsH-bonded species. The subsequent course of each reaction and the final arsenic-containing product distribution depended upon the original AL:N stoichiometric ratio and the respective aminoarsine. When the Al:N ratio was 1:1, the reactions were straightforward for each aminoarsine. However, in every case, [Me2AlNMe2]2 was the final AlN-containing product. Independent reactions were carried out to verify many of the proposed decomposition pathways that lead to thermodynamically stable products. The results of this study are compared with those of the analogous, previously reported (Me3Al)2-aminoarsine systems. Additionally, a new synthetic route to [Me2AlAsMe2]3 has been established from the reaction of (Me2AlH)3 with Me2AsH. © 1994.