RELATIONSHIP BETWEEN INTRAMOLECULAR CHEMICAL-EXCHANGE AND NMR-OBSERVED RATE CONSTANTS

被引:127
作者
GREEN, MLH [1 ]
WONG, LL [1 ]
SELLA, A [1 ]
机构
[1] UNIV LONDON UNIV COLL,DEPT CHEM,CHRISTOPHER INGOLD LABS,LONDON WC1H 0AJ,ENGLAND
关键词
D O I
10.1021/om00043a059
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
This paper shows that the rate constants measured by dynamic NMR methods differ from those of the chemical process(es) giving rise to the exchange and that the chemical rate constants one can derive depend on the mechanism under consideration. Thus, the indiscriminate use of measured rate constants can in unfavorable cases lead to serious errors and consequent incorrect mechanistic interpretation. A simplified method for obtaining rate constants from dynamic NMR experiments in which the exchange processes are defined by more than a single rate-limiting step is described. In addition, the method can be used in the construction of kinetic (Kubo-Sack) matrices.
引用
收藏
页码:2660 / 2668
页数:9
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