32026-93-0Relevant articles and documents
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.
