Electrocatalytic Reduction of CO₂ with Palladium Bis-N-heterocyclic Carbene Pincer Complexes

A series of pyridine- and lutidine-linked bis-N-heterocyclic carbene (NHC) palladium pincer complexes were electrochemically characterized and screened for CO₂ reduction capability with 2,2,2-trifluoroethanol, acetic acid, or 2,2,2-trifluoroacetic acid (TFA) as proton sources. The lutidine-linked pincer complexes electrocatalytically reduce CO₂ to CO at potentials as low as −1.6 V versus Ag/AgNO₃ in the presence of TFA. The one-electron reduction of these complexes is shown to be chemically reversible, yielding a monometallic species, with density functional theory studies indicating charge storage on the redox-active ligand, thus addressing a major source of deactivation in earlier triphosphine electrocatalysts