Oxidatively Induced Reductive Elimination for Methyl Group Transfer via Isolable Transmetalation Complexes

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 CC 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 CC bond formation.

Automated summary

This study describes the mechanistic details of the oxidatively induced reductive elimination of isolated methyl iridium and ruthenium metallacycle complexes. External oxidation was shown to facilitate the challenging CC bond formation under mild conditions. Computational analyses supported a high-valent pathway where the energy barrier for reductive elimination decreases significantly upon metallic oxidation to promote the desired CC bond formation.