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隧穿控制化学反应:第三个反应性范例。

Tunneling Control of Chemical Reactions: The Third Reactivity Paradigm.

机构信息

Institute of Organic Chemistry, Justus-Liebig University , Heinrich-Buff-Ring 17, 35392 Giessen, Germany.

出版信息

J Am Chem Soc. 2017 Nov 1;139(43):15276-15283. doi: 10.1021/jacs.7b06035. Epub 2017 Oct 23.

DOI:10.1021/jacs.7b06035
PMID:29028320
Abstract

This Perspective describes the emergence of tunneling control as a new reactivity paradigm in chemistry. The term denotes a tunneling reaction that passes through a high but narrow potential energy barrier, leading to formation of a product that would be disfavored if the reaction proceeded by passage over kinetic barriers rather than through them. This reactivity paradigm should be considered along with thermodynamic and kinetic control as a factor that can determine which of two or more possible products is likely to be the one obtained. Tunneling control is a concept that can provide a deep and detailed understanding of a variety of reactions that undergo facile (and possibly unrecognized) tunneling.

摘要

本文观点阐述了隧穿控制作为化学中一个新的反应性范例的出现。这个术语表示一种隧穿反应,它穿过一个高但狭窄的势能障碍,导致形成一种产物,如果反应不是通过穿过动力学障碍而是通过它们来进行,产物将是不利的。这种反应性范例应该与热力学和动力学控制一起被认为是可以决定两个或更多可能产物中哪一个可能是得到的产物的因素之一。隧穿控制是一个可以提供对各种经历容易(可能未被认识到)隧穿的反应的深刻和详细理解的概念。

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