The first electrochemical approach for nickel‐catalyzed cross‐electrophile coupling was developed. This method provides a novel route to 1,1‐diarylalkane derivatives from simple and readily available alkyl and aryl halides in good yields and excellent regioselectivity under mild conditions. The procedure shows good tolerance for a broad variety of functional groups and both primary and secondary alkyl halides can be used. Furthermore, the reaction was successfully scaled up to the multigram scale, thus indicating potential for industrial application. Mechanistic investigation suggested the formation of a nickel hydride in the electroreductive chain‐walking arylation, which led to the development of a new nickel‐catalyzed hydroarylation of styrenes to provide a series of 1,1‐diaryl alkanes in good yields under mild reaction conditions.

Hydride transfers are key to a number of economically and environmentally important reactions, including H2 evolution and NADH regeneration. Therefore, the electrochemical generation of reactive hydrides has the potential to drive the electrification of chemical reactions to improve their sustainability for a green economy. Catalysts containing molybdenum (Mo) have recently been recognized as amongst the most promising non-precious catalysts for H2 evolution, but the mechanism of Mo in conferring this activity remains debated. In this work, we use a modified EPR setup to demonstrate the presence and catalytic role of a trapped Mo 3+ hydride in amorphous Mo sulfide (a-MoSx), one of the most active non-noble H2 evolution catalysts yet reported. We further confirm that this hydride is active for the selective electrochemical hydrogenation of the biologically important energy carrier NAD to its active NADH form and therefore utilized for biocatalysis, and that this reactivity applies to other HER-active forms of Mo sulfide. Our results represent the first direct experimental evidence of an immediate role for Mo in heterogeneous H2 evolution, placing a paramagnetic Mo center, as opposed to its partner atoms, 2 as an HER-active site with uniquely high activity for hydride formation and transfer. This mechanistic finding also reveals that Mo sulfides have potential as economic electrocatalysts for NADH regeneration in biocatalysis.

A protocol for the fast and selective two-electron reduction of the potent greenhouse gas sulfur hexafluoride (SF6) by organic electron donors at ambient temperature has been developed.

A new and safe method for the synthesis of N-(trifluoromethylthio)phthalimide, a convenient and shelf-stable reagent for the direct trifluoromethylthiolation, has been developed. N-(Trifluoromethylthio)phthalimide can be used as an electrophilic source of F3 CS(+) and reacts readily with boronic acids and alkynes under copper catalysis. The utility of CF3 S-containing molecules as biologically active agents, the mild reaction conditions employed, and the high tolerance of functional groups demonstrate the potential of this new methodology to be widely applied in organic synthesis as well as industrial pharmaceutical and agrochemical research and development.