Fragmentation of aryl halide π anion radicals.: Bending of the cleaving bond and activation vs driving force relationships

被引：151

作者：

Costentin, C ^{[1
]}

Robert, M ^{[1
]}

Savéant, JM ^{[1
]}

机构：

[1] Univ Paris 07, CNRS, UMR 7591, Electrochim Mol Lab, F-75251 Paris 05, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 49期

关键词：

D O I：

10.1021/ja045989u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Recent rate data for very fast cleaving of aryl chloride and bromide anion radicals may be accommodated satisfactorily within rate constant versus ArX/ArX.- standard potential existing correlations provided the standard potential is determined experimentally. Cyclic voltammetry is used for this purpose, taking careful account of the electron transfer/fragmentation reaction mixed character of the kinetics. The ensuing activation/driving force relationships allow the determination of the intrinsic barriers, the magnitude of which are discussed in the framework of a new Morse curve model that includes and emphasizes the role of bond bending.

引用

页码：16051 / 16057

页数：7

共 56 条

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