%0 Journal Article %A Wang, Dongyang %A Leng, Xuebing %A Ye, Shengfa %A Deng, Liang %D 2019 %T Substrate Redox Non-innocence Inducing Stepwise Oxidative Addition Reaction: Nitrosoarene C–N Bond Cleavage on Low-Coordinate Cobalt(0) Species %U https://acs.figshare.com/articles/journal_contribution/Substrate_Redox_Non-innocence_Inducing_Stepwise_Oxidative_Addition_Reaction_Nitrosoarene_C_N_Bond_Cleavage_on_Low-Coordinate_Cobalt_0_Species/8083187 %R 10.1021/jacs.9b03726.s001 %2 https://acs.figshare.com/ndownloader/files/15074891 %K organo-nitrogen compounds %K Substrate Redox Non-innocence Inducing Stepwise Oxidative Addition Reaction %K IPr %K redox non-innocence %K bond %K transition-metal species %K ONAr %K oxidative %K cobalt nitrosyl aryl %K metal-catalyzed transformations %K nitroso %K Spectroscopic characterizations %K DFT calculations %X 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. %I ACS Publications