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Mechanism of Ni-Catalyzed Oxidations of Unactivated C(sp<sup>3</sup>)-H Bonds.


ABSTRACT: The Ni-catalyzed oxidation of unactivated alkanes, including the oxidation of polyethylenes, by meta-chloroperbenzoic acid (mCPBA) occur with high turnover numbers under mild conditions, but the mechanism of such transformations has been a subject of debate. Putative, high-valent nickel-oxo or nickel-oxyl intermediates have been proposed to cleave the C-H bond, but several studies on such complexes have not provided strong evidence to support such reactivity toward unactivated C(sp3)-H bonds. We report mechanistic investigations of Ni-catalyzed oxidations of unactivated C-H bonds by mCPBA. The lack of an effect of ligands, the formation of carbon-centered radicals with long lifetimes, and the decomposition of mCPBA in the presence of Ni complexes sugg

SUBMITTER: Qiu Y 

PROVIDER: S-EPMC11620755 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature