Reaction of stable phosphinyl radical la with AZADO gave aminoxyphosphine 3 as the primary product by selective radical coupling at -40 degrees C. Compound 3 decomposed to phosphorane 4, silyl phosphinate 5, and aminophosphine 6 at room temperature. The molecular structures of 4-6 were determined by X-ray structural analysis. The homolytic N-O bond cleavage of 3 and the subsequent silyl migration of the resulting phosphinoyl radical 7 would be key steps in the reaction.