814-97-1Relevant academic research and scientific papers
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.
Mixed-valence derivatives of phosphorus sulfides. Two new isomeric thiophosphoryl-μ-thio-phosphines containing fluorine and trifluoromethyl substituents and a discussion of their exchange properties
Doty, Leon F.,Cavell, Ronald G.
, p. 2722 - 2729 (2007/10/14)
Two new mixed-valence phosphorus compounds F2P(S)SP(CF3)2 and (CF3)2P(S)SPF2 are formed by the reaction of the acids F2PS2H or (CF3)2PS2H with the aminophosphines (CF3)2PN(CH3)2 or F2PN(CH3)2, respectively. Temperature-dependent nmr spectroscopy demonstrates the presence of an exchange process which destroys P-P coupling at room temperature in (CF3)2P(S)SPF2 but not in F2P(S)SP(CF3)2. The directly bound substituents are not interchanged by the exchange process and phosphorus valence is maintained. Concentration-dependent nmr studies indicate an intermolecular process and a plausible bimolecular process is described which accounts for the exchange process in X2P(S)SPX2 (X = F, CF3) molecules. When combined, the two new mixed-valence compounds equilibrate to form the two known symmetrically substituted isomers F2P(S)SPF2 and (CF3)2P(S)SP(CF3)2 and the equilibrium mixture can also be approached from these compounds. Thermal stability trends indicate a lower stability for compounds containing the PF2 moiety. Chemical reaction with protic species occurs with cleavage at the PIII-S link to yield phosphines and the parent acid and with halogens to yield halogeno phosphines and thiophosphinates. The reactions with mercury yield dithiophosphinato complexes and diphosphines or their decomposition products. Alkaline hydrolysis of CF3 species proceeds to yield 2 mol of CF3H per CF3 phosphino group and 1 mol per thiophosphinato group.
