Trifluoronitrosomethane reacts with trifluoromethylarsine and bis(trifluoromethyl)arsine to afford CF 3 As[OBN(H)CF 3 ] 2 (A) and (CF 3 ) 2 AsON(H)CF 3 (B), respectively. Compound B has been found to decompose at 60 °C to give (CF 3 ) 2 As(O)H, (CF 3 ) 2 AsOH and (CF 3 ) 2 AsF. The reactions of both A and B with anhydrous hydrogen chloride result in the cleavage of the As-O bond to afford quantitative yields of the respective arsenic chloride. Reactions of B with bis(trifluoromethyl)nitroxyl gives (CF 3 ) 2 AsON(CF 3 ) 2 , (CF 3 ) 2 NOH, (CF 3 ) 2 NH, CF 3 NO 2 , CF 3 NO and a non-volatile white solid.