Computational Organic Electrosynthesis: The Role of Overcharge Protectors

Organic electrosynthesis is a powerful technique that provides enhanced yields along with key advantages such as atom economy, sustainability, and improved selectivity. However, its comprehensive mechanistic understanding remains challenging due to its complex and often non‐trivial nature. Herein, a complete computational investigation of a nickel‐catalyzed electrochemical cross electrophile coupling reaction is reported, previously reported by Sevov and coworkers, which is facilitated by an overcharge protector. Our approach combines density functional theory calculations with microkinetic modeling to first elucidate the reaction mechanism in solution and then to characterize the electrodic processes, where the catalyst degradation competes with protector reduction. To account for this competition, the electric current is incorporated into the microkinetic simulations by defining the electron transfer rate. All components are integrated into the model, simulating the reaction both with and without the protector, achieving good reproduction of the experimental results and leading to a better understanding of its mechanistic features.