Encounter geometry determines product characteristics of electron transfer from 4-hydroxythiophenol to n-butyl chloride radical cations

被引:17
作者
Dey, GR
Hermann, R
Naumov, S
Brede, O [1 ]
机构
[1] Bhabha Atom Res Ctr, Div Appl Chem, Chem Grp, Bombay 400085, Maharashtra, India
[2] Univ Leipzig, Interdisciplinary Grp Time Resolved Spect, D-04303 Leipzig, Germany
[3] Inst Surface Modificat, D-04303 Leipzig, Germany
关键词
D O I
10.1016/S0009-2614(99)00738-1
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 electron transfer reaction between the n-butyl chloride parent ion and if-thiophenol was studied using pulse radiolysis in solutions of 4-thiophenol in n-butyl chloride. It was found to have a diffusion-controlled rate constant of 1.5 X 10(10) dm(3) mol(-1) s(-1) and to involve contributions from all functional groups, i.e. -SH, -OH and the aromatic ring. Consequently, thiyl and phenoxyl radicals and 4-hydroxythiophenol radical cations were observed as direct products of this ion-molecule reaction. This unexpected reaction behavior could be explained by the hypothesis that the encounter geometry of the reaction partners determines the product characteristics. (C) 1999 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:137 / 144
页数:8
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