Absolute rate constants of alkene addition reactions of a fluorinated radical in water

被引：21
|
作者：
Zhang, L
Dolbier, WR [1 ]
Sheeller, B
Ingold, KU
机构：
[1] Univ Florida, Dept Chem, Gainesville, FL 32611 USA
[2] Natl Res Council Canada, Ottawa, ON K1A 0R6, Canada
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 22期
关键词：
D O I：
10.1021/ja0256010
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Absolute rate constants of .RfSO(3)(-) radical addition to a series of water-soluble alkenes containing ionic, carboxylate substituents were measured by laser flash photolysis experiments in water. The observed rate constants were all considerably larger than those of structurally similar analogues in a nonpolar organic solvent, with rate factors of 3-9-fold being observed. It is concluded that such rate enhancements derive at least in part from stabilization of the polar transition state for addition of the electrophilic fluorinated radical to alkenes by the polar solvent water.
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页码：6362 / 6366
页数：5
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