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Ab initio MO study of the solvent effect on the SN2 reaction of the trimethylsulfonium cation with chloride anion

✍ Scribed by Osamu Kikuchi; Yoko Sano; Ohgi Takahashi; Kenji Morihashi

Publisher: John Wiley and Sons
Year: 1996
Tongue: English
Weight: 524 KB
Volume: 7
Category: Article
ISSN: 1042-7163
DOI: 10.1002/(sici)1098-1071(199608)7:4<273::aid-hc10>3.0.co;2-o

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✦ Synopsis

A recently developed ab initio MO theory including solvent effects has been applied to a typical cation-anion reaction, the SN2 reaction of the trimethylsulfonium cation with the chloride anion. In the gas phase, the trimethylsulfonium and chloride ions are unstabilized, and the reaction is expected to proceed rapidly. In aqueous solution, the reactant ions are largely stabilized, and the reaction has been predicted to be endothermic, with an activation energy of 30-40 kcallmol. This potential energy profile, which agrees with experimental results, has been well elucidated by differential solvation at several stages of the reaction path. At the transition state of this reaction, the C and H atoms in the transferring CH, group are almost in a plane that is perpendicular to the Cl-C-S line, reflecting the con- certed nature of the reaction. The population analysis has shown that the electrons in the C-S bond are mostly withdrawn by the sulfur atom at the transition state and that the electron transfer from Cl to CH, occurs after the transition state. The calculated activation energy for the reaction in ethanol is smaller than that in water This agrees with experiments.

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