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Korean Chemical Society (대한화학회)
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Correlation of the Rates of Solvolysis of Diphenylthiophosphinyl Chloride Using an Extended form of the Grunwald-Winstein Equation

  • Koh, Han-Joong (Department of Science Education, Chonju National University of Education) ;
  • Kang, Suk-Jin (Department of Science Education, Chonju National University of Education) ;
  • Kevill, Dennis N. (Department of Chemistry and Biochemistry, Northern Illinois University)
  • Published : 2008.10.20
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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 $SN_2$ pathway is proposed for the solvolyses of diphenylthiophosphinyl chloride. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for an $S_N2$ reaction.

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References

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