Abstract
Herein, we describe the mechanistic details on the oxidatively induced reductive elimination of isolated methyl iridium and ruthenium metallacycle complexes. It was demonstrated that the otherwise challenging C─C bond formation is indeed facilitated by external oxidation, being enabled under mild conditions. Computational analyses supported the proposed high‐valent pathway, where the energy barrier for reductive elimination significantly decreases upon the metallic oxidation to facilitate the desired C─C bond formation.
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