Mechanistic Insight into the O₂ Evolution Catalyzed by Copper Complexes with Tetra- and Pentadentate Ligands

The mononuclear complexes ([(bztpen)Cu] (BF₄)₂ (bztpen = N-benzyl-N,N',N'-tris (pyridin-2-yl methyl ethylenediamine))) and ([(dbzbpen)Cu(OH₂)] (BF₄)₂ (dbzbpen = N,N'-dibenzyl-N,N'-bis(pyridin-2-ylmethyl) ethylenediamine)) have been reported as water oxidation catalysts in basic medium (pH = 11.5). We explore the O₂ evolution process catalyzed by these copper catalysts with various ligands (L) by applying the first-principles molecular dynamics simulations. First, the oxidation of catalysts to the metal-oxo intermediates [LCu(O)]²⁺ occurs through the proton-coupled electron transfer (PCET) process. These intermediates are involved in the oxygen-oxygen bond formation through the water-nucleophilic addition process. Here, we have considered two types of oxygen-oxygen bond formation. The first one is the transfer of the hydroxide of the water molecule to the Cu═O moiety; the proton transfer to the solvent leads to the formation of the peroxide complex ([LCu(OOH)]⁺). The other is the formation of the hydrogen peroxide complex ([LCu(HOOH)]²⁺) by the transfer of proton and hydroxide of the water molecule to the metal-oxo intermediate. The formation of the peroxide complex requires less activation free energy than hydrogen peroxide formation for both catalysts. We found two transition states in the well-tempered metadynamics simulations: one for proton transfer and another for hydroxide transfer. In both cases, the proton transfer requires higher free energy. Following the formation of the oxygen-oxygen bond, we study the release of the dioxygen molecule. The formed peroxide and hydrogen peroxide complexes are converted into the superoxide complex ([LCu(OO)]²⁺) through the transfer of proton, electron, and PCET processes. The superoxide complex releases an oxygen molecule upon the addition of a water molecule. The free energy of activation for the release of the dioxygen molecule is lesser than that of the oxygen-oxygen bond formation. When we observe the entire water oxidation process, the oxygen-oxygen bond formation is the rate-determining step. We calculated the rates of reaction by using the Eyring equation and found them to be close to the experimental values.