Enhanced Electrochemical CO2 Reduction by a Series of Molecular Rhenium Catalysts Decorated with Second-Sphere Hydrogen-Bond Donors

Abstract

A series of rhenium(I) fac-tricarbonyl complexes containing pendent arylamine functionality in the second coordination sphere have been developed and studied as electrocatalysts for carbon dioxide (CO₂) reduction. Aniline moieties were appended at the 6 position of a 2,2'-bipyridine (bpy) donor in which the primary amine was positioned at the ortho- (1-Re), meta- (2-Re), and para- (3-Re) sites of the aniline substituent to generate a family of isomers. The relationship between the catalyst structure and activity was explored across the series, and the catalytic performance was compared to that of the benchmark catalyst Re(bpy)(CO)₃Cl (ReBpy). Catalysts 1-Re, 2-Re, and 3-Re outperform the benchmark catalyst both in anhydrous acetonitrile and with added trifluoroethanol (TFE) as an external proton source. In the presence of TFE, the aniline-substituted catalysts convert CO₂ to carbon monoxide (CO) with high Faradaic efficiencies (≥89%) and have superior turnover frequencies (TOFs) relative to ReBpy (72.9 s^-1), with 2-Re having the highest TOF of the series at 239 s^-1, a value that is twice that of the next most active catalyst. TOFs of 123 and 109 s^-1 were observed for the ortho- and para-substituted aniline complexes (1-Re and 3-Re), respectively. Indeed, catalytic activities vary widely across the series, showing a high sensitivity to the position of the amine functionality relative to the rhenium active site. IR and UV-vis spectroelectrochemical experiments were conducted on the aniline-substituted systems, revealing important differences between the catalysts and mechanistic insight.