Judicious Ligand Design in Ruthenium Polypyridyl CO₂Reduction Catalysts to Enhance Reactivity by Steric and Electronic Effects

A series of Ru^IIpolypyridyl complexes of the structural design [Ru^II(R−tpy)(NN)(CH₃CN)]²⁺(R−tpy=2,2′:6′,2′′-terpyridine (R=H) or 4,4′,4′′-tri-tert-butyl-2,2′:6′,2′′-terpyridine (R=tBu); NN=2,2′-bipyridine with methyl substituents in various positions) have been synthesized and analyzed for their ability to function as electrocatalysts for the reduction of CO₂to CO. Detailed electrochemical analyses establish how substitutions at different ring positions of the bipyridine and terpyridine ligands can have profound electronic and, even more importantly, steric effects that determine the complexes’ reactivities. Whereas electron-donating groups para to the heteroatoms exhibit the expected electronic effect, with an increase in turnover frequencies at increased overpotential, the introduction of a methyl group at the ortho position of NN imposes drastic steric effects. Two complexes, [Ru^II(tpy)(6-mbpy)(CH₃CN)]²⁺(trans-[3]²⁺; 6-mbpy=6-methyl-2,2′-bipyridine) and [Ru^II(tBu−tpy)(6-mbpy)(CH₃CN)]²⁺(trans-[4]²⁺), in which the methyl group of the 6-mbpy ligand is trans to the CH₃CN ligand, show electrocatalytic CO₂reduction at a previously unreactive oxidation state of the complex. This low overpotential pathway follows an ECE mechanism (electron transfer–chemical reaction–electron transfer), and is a direct result of steric interactions that facilitate CH₃CN ligand dissociation, CO₂coordination, and ultimately catalytic turnover at the first reduction potential of the complexes. All experimental observations are rigorously corroborated by DFT calculations.