Marcus Analysis of Ambident Reactivity

被引：47
|
作者：
Breugst, Martin [1 ]
Zipse, Hendrik [1 ]
Guthrie, J. Peter [2 ]
Mayr, Herbert [1 ]
机构：
[1] Univ Munich, Dept Chem, D-81377 Munich, Germany
[2] Univ Western Ontario, London, ON N6A 3K7, Canada
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2010年 / 49卷 / 30期
关键词：
ab initio calculations; computational chemistry; Marcus theory; nucleophilic substitution; transition states; ELECTRON-TRANSFER REACTIONS; MODEL S(N)2 REACTIONS; SOFT ACIDS; INTRINSIC BARRIERS; SN2; REACTIONS; LEAST MOTION; BASES HSAB; CH3X+F-X; HARD; PRINCIPLE;
D O I：
10.1002/anie.201001574
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A better approach to ambident reactivity: The principle of hard and soft acids and bases (HSAB) cannot rationalize the reactivities of even the prototypical ambident nucleophiles shown in the picture. Marcus theory, which describes activation energies by a combination of intrinsic and thermodynamic terms, is a superior alternative. © 2010 Wiley-VCH Verlag GmbH & Co.KGaA.
引用
收藏
页码：5165 / 5169
页数：5
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