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元素周期表中的挫败:金属配合物对氢气的异裂

Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes.

作者信息

Bullock R Morris, Chambers Geoffrey M

机构信息

Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory, PO Box 999, K2-12, Richland, WA 99352, USA

Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory, PO Box 999, K2-12, Richland, WA 99352, USA.

出版信息

Philos Trans A Math Phys Eng Sci. 2017 Aug 28;375(2101). doi: 10.1098/rsta.2017.0002.

Abstract

This perspective examines frustrated Lewis pairs (FLPs) in the context of heterolytic cleavage of H by transition metal complexes, with an emphasis on molecular complexes bearing an intramolecular Lewis base. FLPs have traditionally been associated with main group compounds, yet many reactions of transition metal complexes support a broader classification of FLPs that includes certain types of transition metal complexes with reactivity resembling main group-based FLPs. This article surveys transition metal complexes that heterolytically cleave H, which vary in the degree that the Lewis pairs within these systems interact. Many of the examples include complexes bearing a pendant amine functioning as the base with the metal functioning as the hydride acceptor. Consideration of transition metal compounds in the context of FLPs can inspire new innovations and improvements in transition metal catalysis.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.

摘要

本文从过渡金属配合物对氢的异裂反应角度审视受阻路易斯酸碱对(FLP),重点关注含有分子内路易斯碱的分子配合物。传统上,FLP与主族化合物相关联,但过渡金属配合物的许多反应支持对FLP进行更广泛的分类,其中包括某些类型的过渡金属配合物,其反应活性类似于基于主族的FLP。本文综述了能异裂氢的过渡金属配合物,这些配合物中路易斯酸碱对之间的相互作用程度各不相同。许多例子包括带有侧链胺作为碱、金属作为氢化物受体的配合物。在FLP背景下考虑过渡金属化合物可以激发过渡金属催化领域的新创新和改进。本文是主题为“受阻路易斯酸碱对化学”特刊的一部分。

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