The compounds [formula] and [formula] readily undergo transamination in the presence of ammonia, primary amines, and secondary amines at room temperature. The high lability of the aminoarsolane arsenic-nitrogen bond in the presence of a species containing the weakly protonic N-H group and the equilibrium nature of this transamination reaction permit an easy synthetic route to a variety of aminoarsolanes in high yields. In the reaction of NH3 and [formula], the novel diarsolanylamines are obtained. From the reactions of NH3 and [formula] are isolated, respectively. These results are discussed relative to a reaction pathway that includes Lewis acid-base interactions at the -O-AsN-H sites on arsolane derivatives. The mass spectral data, fragment ion identities, and fragmentation modes are given for the two series of aminoarsolanes. Molecular ion elimination of a dialkylamino group to yield the respective arsenium ion, [formula], is observed in the electron impact induced fragmentation of the aminoarsolanes. Formation of the R2NAs+ ion via aldehyde elimination processes is also an important route for the [formula] but not the [formula] compounds. © 1980, American Chemical Society. All rights reserved.