Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier/CNRS UMR 5069, 118 Route de Narbonne, 31062 Toulouse Cedex 09 (France).
Current address: Department of Chemistry and Pharmaceutical Sciences, VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands).
Angew Chem Int Ed Engl. 2015 Dec 7;54(50):15022-45. doi: 10.1002/anie.201506271. Epub 2015 Nov 13.
For a while, the reactivity of gold complexes was largely dominated by their Lewis acid behavior. In contrast to the other transition metals, the elementary steps of organometallic chemistry-oxidative addition, reductive elimination, transmetallation, migratory insertion-have scarcely been studied in the case of gold or even remained unprecedented until recently. However, within the last few years, the ability of gold complexes to undergo these fundamental reactions has been unambiguously demonstrated, and the reactivity of gold complexes was shown to extend well beyond π-activation. In this Review, the main achievements described in this area are presented in a historical context. Particular emphasis is set on mechanistic studies and structure determination of key intermediates. The electronic and structural parameters delineating the reactivity of gold complexes are discussed, as well as the remaining challenges.
有一段时间,金配合物的反应性在很大程度上受其路易斯酸行为的支配。与其他过渡金属相比,有机金属化学的基本步骤——氧化加成、还原消除、转移金属化、迁移插入——在金的情况下几乎没有被研究过,甚至直到最近才出现。然而,在过去的几年中,金配合物进行这些基本反应的能力已经得到了明确的证明,并且金配合物的反应性已经远远超出了π-活化。在这篇综述中,以历史背景介绍了该领域所描述的主要成就。特别强调了对关键中间体的机理研究和结构测定。讨论了描述金配合物反应性的电子和结构参数,以及仍然存在的挑战。