C(sp3)‑CF3 Reductive Elimination from a Five-Coordinate Neutral Copper(III) Complex

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...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2020-05, Vol.142 (21), p.9785-9791
Main Authors: Liu, Shuanshuan, Liu, He, Liu, Shihan, Lu, Zehai, Lu, Changhui, Leng, Xuebing, Lan, Yu, Shen, Qilong
Format: Article
Language:English
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Summary: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 CH3-CF3 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.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.0c03304