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主族路易斯酸促进的过渡金属氢化物配合物的转化。

Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes.

机构信息

Department of Chemistry, University of Houston , Lamar Fleming Jr. Building, 3585 Cullen Boulevard, Room 112, Houston, Texas 77204-5003, United States.

出版信息

Chem Rev. 2016 Aug 10;116(15):8873-911. doi: 10.1021/acs.chemrev.6b00034. Epub 2016 May 10.

Abstract

This Review highlights stoichiometric reactions and elementary steps of catalytic reactions involving cooperative participation of transition-metal hydrides and main group Lewis acids. Included are reactions where the transition-metal hydride acts as a reactant as well as transformations that form the metal hydride as a product. This Review is divided by reaction type, illustrating the diverse roles that Lewis acids can play in mediating transformations involving transition-metal hydrides as either reactants or products. We begin with a discussion of reactions where metal hydrides form direct adducts with Lewis acids, elaborating the structure and dynamics of the products of these reactions. The bulk of this Review focuses on reactions where the transition metal and Lewis acid act in cooperation, and includes sections on carbonyl reduction, H2 activation, and hydride elimination reactions, all of which can be promoted by Lewis acids. Also included is a section on Lewis acid-base secondary coordination sphere interactions, which can influence the reactivity of hydrides. Work from the past 50 years is included, but the majority of this Review focuses on research from the past decade, with the intent of showcasing the rapid emergence of this field and the potential for further development into the future.

摘要

这篇综述重点介绍了涉及过渡金属氢化物和主族路易斯酸协同参与的计量反应和催化反应的基本步骤。其中包括过渡金属氢化物作为反应物的反应以及形成金属氢化物作为产物的转化。这篇综述按反应类型进行划分,说明了路易斯酸在作为反应物或产物的过渡金属氢化物介导转化中可以发挥的多种作用。我们首先讨论了金属氢化物与路易斯酸直接形成加合物的反应,详细阐述了这些反应产物的结构和动力学。本综述的大部分内容集中在过渡金属和路易斯酸协同作用的反应上,包括羰基还原、H2 活化和氢化物消除反应等章节,这些反应都可以被路易斯酸促进。还包括一个关于路易斯酸碱二次配位球相互作用的部分,它可以影响氢化物的反应性。综述中包括了过去 50 年的工作,但大部分内容集中在过去十年的研究上,旨在展示该领域的快速发展以及未来进一步发展的潜力。

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