Mechanistic Insights into Cobalt-Based Water Oxidation Catalysis by DFT-Based Molecular Dynamics Simulations

We report the mechanistic details of the water oxidation process by the complex, [Co^II(bpbH₂)Cl₂], where bpbH₂ = N, N'-bis(2'-pyridinecarboxamide)-1,2-benzene. An experimental study reported the complex as the efficient catalyst for the water oxidation process. We performed density functional theory calculations at the M06-L level and first-principles molecular dynamics simulations to study the catalytic nature of the complex. We investigated the energetics of the total catalytic cycle, which combines the oxygen-oxygen bond formation, proton-coupled electron transfer (PCET) steps, and release of oxygen molecule. The formed peroxide and superoxide intermediates in the catalytic cycle were characterized with the help of the Mulliken spin density parameters. Mulliken spin densities of the metal-oxo bond reveal that the triplet state of Co^V═O has a double-bond nature, but the quintet state of the complex has a radical nature (Co^IV-O^•-). In an alternative way, the deprotonation of the amide groups of the ligand is also considered. The deprotonation and formation of higher oxidation metal-oxo intermediates are also possible. In addition to this, we have considered the effect of phosphate buffer on water nucleophilic addition. The oxygen-oxygen bond formation is favorable by the catalyst with the deprotonated form of the ligand, with the addition of water as the nucleophile. In the oxidation process, the C═O bonds of the ligand transfer the electron density to nitrogen atoms, stabilizing the higher order oxo, peroxide, and superoxide bonds. The oxygen-oxygen bond formation is the rate-determining step in the overall water oxidation process. This bond was further investigated using first-principles molecular dynamics at the PBE-D2 level. The dynamics of proton, hydroxide ion, and the nature of the ligand structure on the oxygen-oxygen bond were examined. We find that the oxygen molecule is released from the superoxide complex with the addition of water molecules.