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Reactions of arene replacement in transition metal complexes

机译：过渡金属配合物中芳烃置换的反应

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摘要

Replacement of an aromatic ligand is a typical reaction of transition metal complexes and understanding of its general features is crucial for their successful application. This review summarizes thermodynamic and kinetic factors that affect the arene replacement. From the thermodynamic viewpoint, electron-poor arenes typically form less stable complexes and therefore are more easily replaced. From the kinetic viewpoint, arene displacement is initiated by nucleophilic attack of the incoming ligand and therefore high positive charge of the metal and its spatial accessibility, as well as donor properties of the incoming ligands facilitate the process. Arene displacement can be accelerated by heating, irradiation or by addition of polar, coordinating solvents. Transition metals of groups 6-8 usually form relatively stable and inert arene complexes, while complexes of metals of groups 4-5 and 9-11 are labile and undergo arene replacement in mild conditions. The application of the arene displacement reaction for the synthesis of various organometallic compounds and generation of catalytically active species is also discussed in the review. (C) 2020 Elsevier B.V. All rights reserved.
机译：芳族配体的取代是过渡金属配合物的典型反应，了解其一般特征对于其成功应用至关重要。这篇综述总结了影响芳烃替代的热力学和动力学因素。从热力学观点来看，贫电子的芳烃通常形成不稳定的络合物，因此更容易被取代。从动力学的观点来看，芳烃的置换是由进入的配体的亲核攻击引发的，因此金属的高正电荷及其空间可及性，以及进入的配体的供体性质促进了这一过程。可以通过加热，辐射或通过添加极性配位溶剂来加速芳烃的置换。 6-8族的过渡金属通常形成相对稳定和惰性的芳烃络合物，而4-5和9-11族的金属络合物不稳定，并在温和条件下进行芳烃置换。综述中还讨论了芳烃置换反应在各种有机金属化合物的合成和催化活性物种的产生中的应用。 （C）2020 Elsevier B.V.保留所有权利。

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  • 来源
    《Coordination chemistry reviews》 |2020年第5期|213238.1-213238.20|共20页
  • 作者

  • 作者单位

    Russian Acad Sci Nesmeyanov Inst Organoelement Cpds 28 Vavilova St Moscow 119991 Russia;

    Russian Acad Sci Nesmeyanov Inst Organoelement Cpds 28 Vavilova St Moscow 119991 Russia|Plekhanov Russian Univ Econ 36 Stremyannyi Pereulok Moscow 117997 Russia;

  • 收录信息 美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    Arene complexes; Substitution reaction; Ligand exchange; Homogeneous catalysis;

    机译：芳烃配合物;取代反应;配体交换;均相催化;

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