Correlation of the Rates of Solvolysis of Diphenylthiophosphinyl Chloride Using an Extended form of the Grunwald-Winstein Equation

Abstract

Rate of solvolysis of diphenylthiophosphinyl chloride in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluoroethanol (TFE) or 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Solvolyses were also carried out in TFE-ethanol mixtures. For five representative solvents, studies were made at several temperatures and activation parameters determined. The 29 solvents gave a reasonably precise extended Grunwald-Winstein equation plot, correlation coefficient (R) of 0.933, which improved to 0.983 when the four TFE-ethanol points were excluded. The sensitivities (l = 1.00 and m = 0.64) were similar to those obtained for dimethyl phosphorochloridate and phosphorochloridothionate and diphenylphosphinyl chloride (1). As with the four previously studied solvolyses, an <TEX>$SN_2$</TEX> pathway is proposed for the solvolyses of diphenylthiophosphinyl chloride. The activation parameters, <TEX>${\Delta}H^{\neq}$</TEX> and <TEX>${\Delta}S^{\neq}$</TEX>, were determined and they are also in line with values expected for an <TEX>$S_N2$</TEX> reaction.