Metal-Ligand Cooperativity via Exchange Coupling Promotes Iron- Catalyzed Electrochemical CO Reduction at Low Overpotentials.

Biological and heterogeneous catalysts for the electrochemical CO reduction reaction (CORR) often exhibit a high degree of electronic delocalization that serves to minimize overpotential and maximize selectivity over the hydrogen evolution reaction (HER). Here, we report a molecular iron(II) system that captures this design concept in a homogeneous setting through the use of a redox non-innocent terpyridine-based pentapyridine ligand (tpyPY2Me). As a result of strong metal-ligand exchange coupling between the Fe(II) center and ligand, [Fe(tpyPY2Me)] exhibits redox behavior at potentials 640 mV more positive than the isostructural [Zn(tpyPY2Me)] analog containing the redox-inactive Zn(II) ion. This shift in redox potential is attributed to the requirement for both an open-shell metal ion and a redox non-innocent ligand. The metal-ligand cooperativity in [Fe(tpyPY2Me)] drives the electrochemical reduction of CO to CO at low overpotentials with high selectivity for CORR (>90%) and turnover frequencies of 100 000 s with no degradation over 20 h. The decrease in the thermodynamic barrier engendered by this coupling also enables homogeneous CO reduction catalysis in water without compromising selectivity or rates. Synthesis of the two-electron reduction product, [Fe(tpyPY2Me)], and characterization by X-ray crystallography, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), variable temperature NMR, and density functional theory (DFT) calculations, support assignment of an open-shell singlet electronic structure that maintains a formal Fe(II) oxidation state with a doubly reduced ligand system. This work provides a starting point for the design of systems that exploit metal-ligand cooperativity for electrocatalysis where the electrochemical potential of redox non-innocent ligands can be tuned through secondary metal-dependent interactions.