814-97-1Relevant articles and documents
Mixed-valence thiophosphorus compounds. Fluoro- and (trifluoromethyl)(thiophosphorylthio)phosphines with chiral phosphorus centers
Cavell, Ronald G.,Doty, Leon F.
, p. 3086 - 3093 (2008/10/08)
Reactions of the acids (CF3)2PS2H and F2PS2H with the fluoro(trifluoromethyl)aminophosphine CF3(F)PN(CH3)2 and the reaction of the new acid F(CF3)P(S)SH with the fluoro- or (trifluoromethyl)aminophosphines X2PN(CH3)2 (X = F, CF3) provide new isomeric (thiophosphorylthio)phosphines XYP(S)SPX′Y′ (X, Y, X′, Y′ = F, CF3) with chiral phosphorus centers. The compounds were characterized chemically and by NMR spectroscopy. Geminal CF3-CF3 (9.0 Hz for CF3 on pentavalent P; 7.2 Hz for CF3 on trivalent P) and F-F (82.5 Hz for F on pentavalent P; 92.5 Hz for F on trivalent P) coupling constants are revealed in the NMR spectra of the molecules as a result of the presence of the chiral phosphorus centers. Directly bound geminal fluorine atoms on trivalent P show large chemical shift difference between the two fluorine atoms (4.4 ppm) accompanied by substantially different 1JPF coupling constants (1370 and 1291 Hz). Similar but smaller differences prevail between geminal CF3 substituents. Reaction of the new acid F(CF3)P(S)SH with CF3(F)PN(CH3)2 gave a mixture of (thiophosphorylthio)phosphine isomers each with two chiral phosphorus centers. Only partial assignment of the major features of this spectrum could be made.
