Three-Electron Two-Centered Bond and Single-Electron Transfer Mechanism of Water Splitting via a Copper-Bipyridine Complex.

We report the atomistic and electronic details of the mechanistic pathway of the oxygen-oxygen bond formation catalyzed by a copper-2,2'-bipyridine complex. Density functional theory-based molecular dynamics simulations and enhanced sampling methods were employed for this study. The thermodynamics and electronic structure of the oxygen-oxygen bond formation are presented in this study by considering the cis -bishydroxo, [Cu III (bpy)(OH) 2 ] + , and cis -(hydroxo)oxo, [Cu IV (bpy)(OH)(═O)] + , complexes as active catalysts. In the cis -bishydroxo complex, the hydroxide transfer requires a higher kinetic barrier than the proton transfer process. In the case of [Cu IV (bpy)(OH)(═O)] + , the proton transfer requires a higher free energy than the hydroxide one. The peroxide bond formation is thermodynamically favorable for the [Cu IV (bpy)(OH)(═O)] + complex compared with the other. The hydroxide ion is transferred to one of the Cu-OH moieties, and the proton is transferred to the solvent. The free energy barrier for this migration is higher than that for the former transfer. From the analysis of molecular orbitals, it is found that the electron density is primarily present on the water molecules near the active sites in the highest occupied molecular orbital (HOMO) state and lowest unoccupied molecular orbital (LUMO) of the ligands. Natural bond orbital (NBO) analysis reveals the electron transfer process during the oxygen-oxygen bond formation. The σ*Cu(d xz )-O(p) orbitals are involved in the oxygen-oxygen bond formation. During the bond formation, three-electron two-centered (3e - -2C) bonds are observed in [Cu III (bpy)(OH) 2 ] + during the transfer of the hydroxide before the formation of the oxygen-oxygen bond.