Abstract
Specific rates of solvolysis involving displacement of chloride from the trivalent phosphorus of chlorodiphenylphosphine (Ph2PCl, 1) are reported for ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluoroethanol (TFE), and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). The 25 solvents give an extended Grunwald–Winstein correlation with an l value of 1.25 ± 0.09, m value of 0.46 ± 0.06, and correlation coefficient (R) of 0.954. The reactions in aqueous acetone were unusually fast, and these data points lie above the plot. Specific rate values are also reported for TFE–ethanol mixtures. For five representative solvents, values were obtained at three additional temperatures and activation parameters are presented. Rather low enthalpies of activation (8.4 to 11.8 kcal mol−1) are accompanied by very negative entropies of activation (−33 to −46 cal mol−1K−1). The kinetic features observed are consistent with an SN2 reaction incorporating appreciable bond formation and bond breaking at the transition state, and they are very similar to those previously observed for diphenylphosphinyl chloride (Ph2POCl).
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