EXCHANGE REACTIONS BETWEEN O-NITROSOBIS(TRIFLUOROMETHYL)HYDROXYLAMINE AND M(CF3)3 (M=P, As and Sb)

Article abstract of DOI:10.1016/S0022-1139(00)80912-4

O-Nitrosobis(trifluoromethyl)hydroxylamine gives novel reactions with tris(trifluoromethyl)-phosphine, -arsine and -stibine to afford mainly the corresponding bis(trifluoromethyl)nitroxyl derivatives.Tris(trifluoromethyl)phosphine affords (CF3)2NOP(O)(CF3)2 and (CF3)2NNO.Tris(trifluoromethyl)arsine also gives (CF3)2NNO in high yield, together with smaller amounts of (CF3)2NOAs(CF3)2, CF3N=CF2, COF2 and a polymeric white solid.With tris(trifluoromethyl)stibine, no oxidation nor addition reactions occurred.Instead, <(CF3)2NO>3Sb and <(CF3)NO>2SbCF3 were obtained in high yields.The stoichiometry of the reactions suggests that the additional amounts of bis(trifluoromethyl)nitroxyl groups bonded to antimony are derived from the trifluoromethyl groups bonded to antimony.Mechanisms to rationalise these reactions are proposed.