MEDIUM EFFECTS IN THE ELECTROREDUCTION OF BENZOPHENONE IN APROTIC-SOLVENTS

被引：52

作者：

FAWCETT, WR

FEDURCO, M

机构：

[1] Department of Chemistry, University of California, Davis

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1993年 / 97卷 / 27期

关键词：

D O I：

10.1021/j100129a025

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The kinetics of electroreduction of benzophenone have been studied at a mercury ultramicroelectrode in seven aprotic solvents. In addition, the temperature dependence of the standard rate constant was determined in three solvents, and the effect of tetraalkylammonium cations on the kinetic parameters was assessed in acetonitrile. On the basis of an analysis of the solvent effects, it is shown that this fast electron-transfer reaction is adiabatic. A model for solvation of the activated complex based on three contiguous spheres corresponding to the two phenyl rings and the carbonyl group is described and used to assess the outer-sphere contribution to the Gibbs activation energy for electron transfer.

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页码：7075 / 7080

页数：6

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