NAD(P)H-NAD(P)+ MODELS .74. ENTROPY-CONTROLLED KINETICS, STEREOCHEMISTRY, AND TUNNELING EFFECT

被引:19
|
作者
OHNO, A
GOTO, M
MIKATA, Y
KASHIWAGI, T
MARUYAMA, T
机构
[1] Institute for Chemical Research, Kyoto University, Uji, Kyoto
关键词
D O I
10.1246/bcsj.64.87
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Kinetics have been studied for the reactions of three NAD(P)H analogs and their 4-deuteriated compounds with 2,6-dichloro- and tetrachloro-1,4-benzoquinones. It has been elucidated that the entropy term occupies 50-90% of the Gibbs energy of activation at 298 K. Thus, the reaction is almost entropy-controlled. For certain combinations of the reducing and oxidizing reagents, quantum mechanical tunneling effect plays a large role to determine the reaction rate. The tunneling effect may be another measure of the sterochemistry.
引用
收藏
页码:87 / 90
页数:4
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