A Redox Transmetalation Step in Nickel-Catalyzed C-C Coupling Reactions

Ni-catalyzed C-H functionalization reactions are becoming efficient routes to access a variety of functionalized arenes, yet the mechanisms of these catalytic C-C coupling reactions are not well understood. Here we report the catalytic and stoichiometric arylation reactions of a nickel(II) metallacycle. Treatment of this species with silver(I)-aryl complexes results in facile arylation, consistent with a redox transmetalation step. Additionally, treatment with electrophilic coupling partners generates C-C and C-S bonds. We anticipate that this redox transmetalation step may be relevant to other coupling reactions that employ silver salts as additives.