Expedited Proton Relay in Enzyme-Inspired Cobaloximes Facilitate Organic Transformations

Developing a water-soluble, oxygen-tolerant, and acid-stable synthetic H₂ production catalyst is vital for renewable energy infrastructure. To access such an effective catalyst, we strategically incorporated enzyme-inspired, multicomponent outer coordination sphere elements around the cobaloxime (Cl-Co-X) core with suitable axial coordination (X). Our cobaloximes with axial imidazole or L-histidine coordination in photocatalytic HAT including the construction of anilines via a non-canonical cross-coupling approach is found superior compared to commonly used cobaloxime catalysts. The reversible Co(II)/Co(I) process is influenced by the axial N ligand's nature. Imidazole/L-histidine with a higher pKa promptly produces H₂ upon irradiation, leading to the improved reactivity compared to previously employed axial (di)chloride or pyridine analogue.