Virtual transition states: making sense of multiple transition states in parallel and series

IF 39 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Ian H. Williams
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引用次数: 0

Abstract

The apparent Gibbs energies of activation for chemical reactions that involve multiple paths in parallel and/or multiple steps in series may involve several transition states (TSs) lying close in energy. The virtual TS is a weighted average of these contributing real TSs, and the weighting factors are easily obtained from the Gibbs energies of these TSs relative to a common reactant state. Examples from organic reaction mechanisms are used to illustrate the concept and its implications for the interpretation of features of complex Hammett plots and of kinetic isotope effects (KIEs). The concept allows for a considerable simplification of the treatment of KIEs for enzymic reactions, and holds promise for the application of modern methods of computational simulation to assist in the interpretation of experimental kinetic investigations of complex mechanisms.

Abstract Image

虚拟过渡状态:理解并行和串联的多个过渡状态
涉及多个平行路径和/或多个串联步骤的化学反应的表观吉布斯活化能可能涉及几个能量相近的过渡态(ts)。虚拟TS是这些实际TS的加权平均值,加权因子很容易从这些TS相对于共同反应物状态的吉布斯能中得到。本文用有机反应机理的例子来说明这一概念及其对解释复杂哈米特图和动力学同位素效应(KIEs)特征的意义。这一概念允许对酶反应的ky处理进行相当大的简化,并有望应用现代计算模拟方法来协助解释复杂机制的实验动力学研究。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Chemical Society Reviews
Chemical Society Reviews 化学-化学综合
CiteScore
80.80
自引率
1.10%
发文量
345
审稿时长
6.0 months
期刊介绍: Chemical Society Reviews is published by: Royal Society of Chemistry. Focus: Review articles on topics of current interest in chemistry; Predecessors: Quarterly Reviews, Chemical Society (1947–1971); Current title: Since 1971; Impact factor: 60.615 (2021); Themed issues: Occasional themed issues on new and emerging areas of research in the chemical sciences
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