C(sp)-CF 还原消除反应：来自五配位中性铜(III)配合物的研究。
C(sp)-CF Reductive Elimination from a Five-Coordinate Neutral Copper(III) Complex.
机构信息
Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China.
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P.R. China.
出版信息
J Am Chem Soc. 2020 May 27;142(21):9785-9791. doi: 10.1021/jacs.0c03304. Epub 2020 May 18.
The reductive elimination from a high-valent late-transition-metal complex for the formation of a carbon-carbon or carbon-heteroatom bond represents a fundamental product-forming step in a number of catalytic processes. While reductive eliminations from well-defined Pt(IV), Pd(IV), Ni(III)/Ni(IV), and Au(III) complexes have been studied, the analogous reactions from neutral Cu(III) complexes remain largely unexplored. Herein, we report the isolation of a stable, five-coordinate, neutral square pyramidal Cu(III) complex that gives CH-CF in quantitative yield via reductive elimination. Mechanistic studies suggest that the reaction occurs through a synchronous bond-breaking/bond-forming process via a three-membered ring transition state.
高价后过渡金属配合物的还原消除反应对于形成碳-碳或碳杂原子键是许多催化过程中的基本产物形成步骤。虽然已经研究了来自定义明确的 Pt(IV)、Pd(IV)、Ni(III)/Ni(IV)和 Au(III)配合物的还原消除反应，但来自中性 Cu(III)配合物的类似反应在很大程度上仍未得到探索。在此，我们报告了一种稳定的、五配位的、中性的四方锥型 Cu(III)配合物的分离，该配合物通过还原消除定量生成 CH-CF。机理研究表明，该反应通过三员环过渡态通过同步的断键/成键过程发生。
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