Co III/II Redox Couples in Cobaloximes Control Hydrogen‐Atom Transfer for Photoredox N ‐Alkylation of Amines with Lead Halide Perovskite

ABSTRACT Photoredox reaction with halide perovskite (CsPbBr 3 ) quantum dots (QDs) can offer a convenient, cost‐effective, and efficient route for the N ‐alkylation of amine with alcohol. Herein, we demonstrate that the cobaloxime complex can direct the product selectivity from imine to amine by controlling the hydrogen atom transfer (HAT) in the photoredox reaction. In the presence of CsPbBr 3 QDs, the photoredox reaction of amine and alcohol produces imine as the major product with a poor yield, while the addition of a cobaloxime complex [Co‐4] in the reaction medium leads to the selective formation of amine as the major product. The equatorial tuning of the ligand environment around Co‐ion leads to the modulation of electronic properties in the cobaloxime complexes, and a negative shift of the Co III/II reduction potential improves the HAT process to increase the yield of the amine.