Substrate Redox Non-innocence Inducing Stepwise Oxidative Addition Reaction: 
Nitrosoarene C–N Bond Cleavage on Low-Coordinate Cobalt(0) Species

Wang, Dongyang; Leng, Xuebing; Ye, Shengfa; Deng, Liang

doi:10.1021/jacs.9b03726

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Substrate Redox Non-innocence Inducing Stepwise Oxidative Addition Reaction: Nitrosoarene C–N Bond Cleavage on Low-Coordinate Cobalt(0) Species

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Ye, Shengfa
Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Wang, D., Leng, X., Ye, S., & Deng, L. (2019). Substrate Redox Non-innocence Inducing Stepwise Oxidative Addition Reaction: Nitrosoarene C–N Bond Cleavage on Low-Coordinate Cobalt(0) Species. Journal of the American Chemical Society, 141(19), 7731-7735. doi:10.1021/jacs.9b03726.

Cite as: https://hdl.handle.net/21.11116/0000-0004-7ABA-2

Abstract

The reactions of nitrosoarenes with transition-metal species are fundamentally important for their relevance to metal-catalyzed transformations of organo-nitrogen compounds in organic synthesis and also the metabolization of nitroarenes and anilines in biology. In addition to the well-known reactivity of metal-mediated N–O bond activation and cleavage of nitrosoarenes, we present herein the first observation of a nitrosoarene C–N bond oxidative addition reaction upon the interaction of a three-coordinate cobalt(0) species [(IPr)Co(vtms)₂] with 2,4,6-tri(tert-butyl)-1-nitroso-benzene (Ar*NO). The reaction produces a cobalt nitrosyl aryl complex, [(IPr)Co(Ar*)(NO)] (1), with a bis(nitrosoarene)cobalt complex, [(IPr)Co(η²-ONAr)(κ¹-O-ONAr)] (2), as an intermediate. Spectroscopic characterizations, DFT calculations, and kinetic studies revealed that the redox non-innocence of nitrosoarene induces a stepwise pathway for the C–N bond oxidative addition reaction.