亚乙烯基金（I）配合物对C(sp )-H键的活化：协同异步过程还是分步过程？
C(sp )-H Bond Activation by Vinylidene Gold(I) Complexes: A Concerted Asynchronous or Stepwise Process?
作者信息
Klein Johannes E M N, Knizia Gerald, Nunes Dos Santos Comprido Laura, Kästner Johannes, Hashmi A Stephen K
机构信息
Department of Chemistry, University of Minnesota, 207 Pleasant St SE, Minneapolis, MN, 55455, USA.
Present Address: Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
出版信息
Chemistry. 2017 Nov 13;23(63):16097-16103. doi: 10.1002/chem.201703815. Epub 2017 Oct 19.
A detailed analysis of the C(sp )-H activation process by vinylidene Au complexes is described based on an intrinsic bond orbital analysis. Based on our analysis this event can be divided into three phases: (i) hydride transfer, (ii) C-C bond formation, and (iii) σ to π rearrangement of the lone pair coordinated to Au. Small perturbations of the system lead to either a concerted asynchronous reaction, or a stepwise reaction featuring an intermediate with a C-H-C three-centre two-electron (3c-2e) bond. The role of π-donating substituents is highlighted and provides a way of controlling reactions of this type in future experimental studies.
基于内在键轨道分析，描述了亚乙烯基金配合物对C(sp )-H活化过程的详细分析。根据我们的分析，该过程可分为三个阶段：(i) 氢化物转移，(ii) C-C键形成，以及(iii) 与金配位的孤对电子的σ到π重排。系统的微小扰动会导致协同的异步反应，或导致具有C-H-C三中心两电子(3c-2e)键中间体的分步反应。突出了π供电子取代基的作用，并为未来实验研究中控制这类反应提供了一种方法。
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