Deciphering the Synchronization of Alternating Current Frequency with the Nickel Catalytic Cycle in Selective C-N Cross-Coupling.

ABSTRACT: Alternating current (AC) electrolysis offers a promising strategy for modulating redox states in metal-catalyzed reactions, yet its mechanistic basis remains poorly understood. Here, we uncover how AC frequency synchronizes with key steps in a Ni-catalyzed cross-coupling cycle to control product selectivity between C-N and C-C coupling. We show that optimal C-N selectivity arises from minimizing the exposure of a key intermediate, Ni^II(Ar)Br, to reducing conditions that otherwise promote off-cycle Ni^I species and undesired C-C homocoupling. By developing a simple cyclic voltammetry-based method, we accurately predict the optimal AC frequency across diverse aryl bromides and amines, eliminating the need for time-consuming trial-and-error reaction optimization. The pred

SUBMITTER: Hazra A 

PROVIDER: S-EPMC12575208 | biostudies-literature | 2025 Sep

REPOSITORIES: biostudies-literature