Iron‐Electrocatalyzed C−H Arylations: Mechanistic Insights into Oxidation‐Induced Reductive Elimination for Ferraelectrocatalysis

Despite major advances, organometallic C−H transformations are dominated by precious 5d and 4d transition metals, such as iridium, palladium and rhodium. In contrast, the unique potential of less toxic Earth‐abundant 3d metals has been underexplored. While iron is the most naturally abundant transition metal, its use in oxidative, organometallic C−H activation has faced major limitations due to the need for superstoichiometric amounts of corrosive, cost‐intensive DCIB as the sacrificial oxidant. To fully address these restrictions, we describe herein the unprecedented merger of electrosynthesis with iron‐catalyzed C−H activation through oxidation‐induced reductive elimination. Thus, ferra‐ and manganaelectro‐catalyzed C−H arylations were accomplished at mild reaction temperatures with ample scope by the action of sustainable iron catalysts, employing electricity as a benign oxidant.