School of Chemistry, University of East Anglia, Norwich Research Park, Norwich NR47TJ, United Kingdom.
Chem Rev. 2021 Jul 28;121(14):8364-8451. doi: 10.1021/acs.chemrev.0c00552. Epub 2020 Sep 23.
Over the past decade the organometallic chemistry of gold(III) has seen remarkable advances. This includes the synthesis of the first examples of several compound classes that have long been hypothesized as being part of catalytic cycles, such as gold(III) alkene, alkyne, CO and hydride complexes, and important catalysis-relevant reaction steps have at last been demonstrated for gold, like migratory insertion and β-H elimination reactions. Also, reaction pathways that were already known, for example the generation of gold(III) intermediates by oxidative addition and their reductive elimination, are much better understood. A deeper understanding of fundamental organometallic reactivity of gold(III) has revealed unexpected mechanistic avenues, which can open when the barriers for reactions that for other metals would be regarded as "standard" are too high. This review summarizes and evaluates these developments, together with applications of gold(III) in synthesis and catalysis, with emphasis on the mechanistic insight gained in these investigations.
在过去的十年中，金（III）的有机金属化学取得了显著的进展。这包括合成了几种长期以来被认为是催化循环一部分的化合物类别的第一个例子，如金（III）烯烃、炔烃、CO 和氢化物配合物，并且最后证明了金的重要催化相关反应步骤，如迁移插入和β-H 消除反应。此外，已经已知的反应途径，例如通过氧化加成生成金（III）中间体及其还原消除，也得到了更好的理解。对金（III）的基本有机金属反应性的更深入了解揭示了意想不到的反应途径，当对于其他金属被认为是“标准”的反应的能垒过高时，这些途径就会出现。这篇综述总结和评估了这些发展，以及金（III）在合成和催化中的应用，重点是在这些研究中获得的对反应机制的深入了解。
