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双金属体系中小分子的活化:协同反应的全景。

Small molecule activation with bimetallic systems: a landscape of cooperative reactivity.

机构信息

Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Consejo Superior de Investigaciones Científicas (CSIC) and University of Sevilla, Avenida Américo Vespucio 49, 41092 Sevilla, Spain.

出版信息

Chem Commun (Camb). 2022 Oct 6;58(80):11220-11235. doi: 10.1039/d2cc04296g.

Abstract

There is growing interest in the design of bimetallic cooperative complexes, which have emerged due to their potential for bond activation and catalysis, a feature widely exploited by nature in metalloenzymes, and also in the field of heterogeneous catalysis. Herein, we discuss the widespread opportunities derived from combining two metals in close proximity, ranging from systems containing multiple M-M bonds to others in which bimetallic cooperation occurs even in the absence of M⋯M interactions. The choice of metal pairs is crucial for the reactivity of the resulting complexes. In this context, we describe the prospects of combining not only transition metals but also those of the main group series, which offer additional avenues for cooperative pathways and reaction discovery. Emphasis is given to mechanisms by which bond activation occurs across bimetallic structures, which is ascribed to the precise synergy between the two metal atoms. The results discussed herein indicate a future landscape full of possibilities within our reach, where we anticipate that bimetallic synergism will have an important impact in the design of more efficient catalytic processes and the discovery of new catalytic transformations.

摘要

人们对双金属协同配合物的设计越来越感兴趣,这是由于它们在键活化和催化方面的潜力,这一特性在金属酶中得到了广泛的应用,也在多相催化领域得到了广泛的应用。本文讨论了将两种金属紧密结合所带来的广泛机会,从含有多个 M-M 键的系统到即使没有 M⋯M 相互作用也会发生双金属协同作用的系统。金属对的选择对于所得配合物的反应性至关重要。在这种情况下,我们不仅描述了结合过渡金属的前景,还描述了主族系列的前景,这些前景为协同途径和反应发现提供了额外的途径。重点介绍了通过双金属结构发生键活化的机制,这归因于两个金属原子之间的精确协同作用。本文讨论的结果表明,我们未来的前景充满了可能性,我们预计双金属协同作用将在设计更高效的催化过程和发现新的催化转化方面产生重要影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/28a0/9536487/3ab36a2c9857/d2cc04296g-f1.jpg

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