Reactions of bis(trifluoromethyl)nitroxyl with hydrides of phosphorus and arsenic

Abstract

The reactions of bis(trifluoromethyl)nitroxyl with the Group 15 hydrides (CF3)nMH3-n (M = P, As; n = 0, 1) in a ratio of 2:1 proceed rapidly via free-radical mechanisms to afford N,N-bis(trifluoromethyl)hydroxylamine and products which can be rationalised in terms of unstable hydride intermediates (CF3)2NOM(CF3)nH2-n. While the reactions with CF3MH2 (M = P, As) yielded mainly CF3M[ON(CF3)2]2 and (CF3)2NOH, those with AsH3 gave [(CF3)2NO]3As, arsenic metal and (CF3)2NOH. On the other hand, the reactions with PH3 gave a mixture of (CF3)2NOH, (CF3)2NH, hydrogen gas and a polymeric yellow solid. © 1992.