Theoretical Study on the Mechanism of the Electrocatalytic CO2 Reduction to Formate by an Iron Schiff Base Complex

The iron(III) chloride compound 6,6 '-di(3,5-ditert-butyl-2-hydroxybenzene)-2,2 '-bipyridine (Fe(tbudhbpy)Cl) can effectively catalyze the electrochemical CO2 reduction in N,N-dimethylformamide. Density functional calculations were conducted to investigate the mechanism and unravel the governing factors of product selectivity. The results suggest that the initial catalyst, Fe(tbudhbpy)Cl (formally FeIII-Cl), undergoes two reduction steps, accompanied by the dissociation of Cl-, leading to the formation of the active ferrous radical intermediate 2 (formally FeI). Without phenol, 2 attacks CO2 to generate the FeIII-carboxylate intermediate FeIII-CO2, followed by a one-electron reduction to generate FeII-CO2, which reacts with another CO2 to produce CO. This aligns with the experimental result that CO is the main product when the phenol is absent. In contrast, when phenol is presented, the triple reduced species 3 is protonated at its ligand N site to yield 3pt(N) (formally Fe0-NH), which subsequently performs a nucleophilic attack on CO2 to afford formate. This process occurs via an orthogonal electron/proton transfer mechanism, where two electrons and one proton are transferred from the ligand to the CO2 moiety. The redox noninnocent nature of the ligand is thus crucial for formate formation, as it facilitates electron and proton shuttling, enabling 3pt(N) to attack CO2 through this unusual mechanism effectively.