Merging Electrolysis and Nickel Catalysis in Redox Neutral Cross-Coupling Reactions: Experiment and Computation for Electrochemically Induced C–P and C–Se Bonds Formation

We have achieved a nickel-catalyzed cross-coupling reaction via concerted paired electrolysis under mild reaction conditions. In this electrochemical transformation, the anodic oxidation of Ni II to Ni III and cathodic reduction of Ni I to Ni 0 occurred simultaneously, resulting in an economical and sustainable cross-coupling protocol. Moreover, we performed mechanistic investigations, achieved by experiments and density functional theory (DFT) calculations for different C–heteroatom bond formations to reveal the catalytic cycle in more detail.