Insights into Cobalta(III/IV/II)‐Electrocatalysis: Oxidation‐Induced Reductive Elimination for Twofold C−H Activation

The merger of cobalt‐catalyzed C−H activation and electrosynthesis provides new avenues for resource‐economical molecular syntheses, unfortunately their reaction mechanisms remain poorly understood. Herein, we report the identification and full characterization of electrochemically generated high‐valent cobalt(III/IV) complexes as crucial intermediates in electrochemical cobalt‐catalyzed C−H oxygenations. Detailed mechanistic studies provided support for an oxidatively‐induced reductive elimination via highly‐reactive cobalt(IV) intermediates. These key insights set the stage for unprecedented cobaltaelectro two‐fold C−H/C−H activation.