Controlled Single-Electron Transfer via Metal-Ligand Cooperativity Drives Divergent Nickel-Electrocatalyzed Radical Pathways.

ABSTRACT: Electrocatalysis enables the construction of C-C bonds under mild conditions via controlled formation of carbon-centered radicals. For sequences initiated by alkyl halide reduction, coordinatively unsaturated Ni complexes commonly serve as single-electron transfer agents, giving rise to the foundational question of whether outer- or inner-sphere electron transfer oxidative addition prevails in redox mediation. Indeed, rational design of electrochemical processes requires the discrimination of these two electron transfer pathways, as they can have outsized effects on the rate of substrate bond activation and thus impact radical generation rates and downstream product selectivities. We present results from combined synthetic, electroanalytical, and computational studies that examine the mech

SUBMITTER: Wuttig A 

PROVIDER: S-EPMC10877625 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature