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自旋交叉及其在有机金属催化中的应用:概念与最新进展

Spin Crossover and Its Application in Organometallic Catalysis: Concepts and Recent Progress.

作者信息

He Peng, Zhu Shou-Fei

机构信息

Frontiers Science Center for New Organic Matter, State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China.

出版信息

Chemistry. 2024 Dec 23;30(72):e202403437. doi: 10.1002/chem.202403437. Epub 2024 Nov 16.

Abstract

Spin crossover is one of the most important properties of open-shell metal complexes. In organometallic catalytic reactions, catalysts can alter reaction kinetics by spin crossover, i. e., accelerating or hindering the reaction progression, as well as altering reaction pathways, modulating the reaction selectivity or promoting new reactions. This personal account outlines the introduction and development of important concepts such as "two-state reactivity" involving spin crossover, and proposes a new concept, "spin-responsive catalysis" to summarize the catalytic processes in which spin effects are present. Finally, the electronic mechanism of spin crossover accelerating the reaction and the role of spin crossover in changing the reaction path and regulating the reaction selectivity are introduced by taking two recent typical iron-catalyzed reactions recently reported by our group as examples.

摘要

自旋交叉是开壳金属配合物最重要的性质之一。在有机金属催化反应中,催化剂可通过自旋交叉改变反应动力学,即加速或阻碍反应进程,以及改变反应途径、调节反应选择性或促进新反应。本个人综述概述了涉及自旋交叉的“双态反应性”等重要概念的引入和发展,并提出了一个新概念“自旋响应催化”,以总结存在自旋效应的催化过程。最后,以我们小组最近报道的两个典型铁催化反应为例,介绍了自旋交叉加速反应的电子机制以及自旋交叉在改变反应路径和调节反应选择性方面的作用。

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