RECENT ADVANCES IN STUDY OF KINETIC HYDROGEN ISOTOPE-EFFECTS
RECENT ADVANCES IN STUDY OF KINETIC HYDROGEN ISOTOPE-EFFECTS
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DOI：
10.1039/cs9740300513
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发表时间：
1974-01-01
影响因子：
46.2
通讯作者：
BELL, RP
中科院分区：
文献类型：
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作者：
BELL, RP
近年来，每年都有数百篇关于氢同位素效应的论文发表，因此，这篇综述仅限于该主题的某些方面。在阐明反应机制的大致轮廓时，没有提到同位素效应的定性或半定量的使用，尽管这种应用现在进入了有机化学家的日常实践。也不会试图处理二次或溶剂同位素效应。在后一类中，关于H20-D20混合物中的反应的密集工作仍在继续，这些反应原则上为解开溶液中平衡所涉及的物种的性质和过渡态的密切性质提供了有趣的可能性。然而，在实践中，这类研究的结果有点令人失望，部分原因是不同可能性之间的区别通常需要非常准确的测量，部分原因是对非常微小的差异的解释对理论处理中必须做出的简化假设造成了一些压力。本综述试图估计现有的实验材料对初级动力学氢同位素的影响，特别是在溶液中，可以在多大程度上通过理论处理来解释。将特别注意KE类型的反应
In recent years several hundred papers have been published annually on the subject of hydrogen isotope effects, and this review is therefore restricted to certain aspects of the subject. No reference is made to the qualitative or semiquantitative use of isotope effects in elucidating the broad outlines of reaction mechanisms, though such applications now enter into the everyday practice of the organic chemist. Nor will any attempt be made to deal with secondary or solvent isotope effects. In the latter category intensive work has continued on reactions in H20-D20 mixtures which in principle offer intriguing possibilities for unravelling both the nature of the species involved in equilibria in solution, and the intimate nature of transition states. 1 In practice, however, the results of such studies have been slightly disappointing, partly because the distinction between different possibilities usually demands very accurate measurements, and partly because the interpretation of very small differences places some strain on the simplifying assumptions which have to be made in the theoretical treatment. The present review attempts to estimate how far the available experimental material on primary kinetic hydrogen isotope eflects, especially in solution, can be accounted for by a theoretical treatment. Particular attention will be given to reactions of the type kE