%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