Mechanism and Electronic Perspective of Oxygen Evolution Reactions Catalyzed by [Fe(OTf)₂(bpbp)]

We performed first-principles molecular dynamics simulations to study the process of water oxidation by iron-based catalyst [Fe(OTf)2(bpbp)] (OTf = triflouromethanesulfonate, bpbp N,N′-bis(2-pyridylmethyl)-2,2′-bipyrrolidine) in an explicit environment at 300 K temperature. Considering [FeV(bpbp)(OH)(O)]+2 as active catalytic species, we explored each step process. To begin with, set up simulation with one intermediate, 191 molecules, and manganese ion electron acceptor. Prior performing metadynamics simulation, equilibrated system through both classical quantum mechanical levels. Post that, first computed free energy oxygen–oxygen bond formation using metadynamic [FeV(bpbp)(OH)(O)]+2. observed that release dioxygen took place successive steps peroxide superoxide complexes. then studied regeneration FeV═O complex three subsequent proton-coupled transfer (PCET) reactions. Lowdin Mulliken spin moments for mechanism. Wannier center analysis get formal charges atoms involved PCET steps; this confirmed occurrence during proton migration molecule. The free-energy barrier obtained from was used calculate redox potentials these Comparing process, found be rate-determining step. cis-OH identified microkinetic