Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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The Effects of Solvation and Polarizability on the Reaction of S-p-Nitrophenyl Thiobenzoate with Various Anionic Nucleophiles

  • Published : 1994.07.20
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Abstract

Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of S-p-nitrophenyl thiobenzoate with various anionic nucleophiles including 6 ${\alpha}$-effect nucleophiles. A good Bronsted correlation has been observed for the reactions with 7 aryloxides. However, p-chlorothiophenoxide and hydroxide ions exhibit significantly positive and negative deviations, respectively, from the Bronsted plot. The deviations are attributed to the effect of polarizability and solvation rather than a change in the reaction mechanism. The ${\alpha}$-effect nuceophiles except highly basic ones demonstrate remarkably enhanced nucleophilicity. The effects of solvation and/or polarizability are proposed to be important for the cause of the ${\alpha}$-effect.

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