Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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The Effect of Solvation and Polarizability on the $\alpha$-Effect: Nucleophilic Substitution Reactions of p-Nitrophenyl Benzoate with Various Anionic Nucleophiles

  • Um Ik-Hwan (Department of Chemistry, Ewha Womans University)
  • Published : 1992.12.20
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Abstract

Second-order rate constants have been determined spectrophotometrically for nucleophilic substitution reactions of p-nitrophenyl benzoate with various anionic nucleophiles including 6 ${\alpha}$ -effect nucleophiles. The logarithmic second-order rate constants for the aryloxides give a good Bronsted correlation with the respective basicity while the ones for p-chlorothiophenoxide and hydroxide exhibit significantly positive and negative deviations, respectivity, from the Bronsted linear line. The deviations are attributed to a solvation effect rather than a change in the reaction mechanism. The ${\alpha}$-effect nucleophiles except highly basic ones demonstrate significantly higher nucleophilicity (the ${\alpha}$ -effect) than would be predicted from the respective basicity. The effect of solvation and polarizability appears to be important for the ${\alpha}$-effect as well as for the reaction rate.

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