Ligand (biochemistry)

Receptor

Electrode

Organic chemistry

Bipyridine

Stereochemistry

Crystal structure

Density functional theory

Catalysis

Computational chemistry

Physical chemistry

Overpotential

Medicinal chemistry

Chemistry

Substituent

Electrochemistry

Biochemistry

Photochemistry

ACS Catalysis

In order to help develop robust and deployable molecular electrocatalysts for the reduction of CO2 to CO, we must understand the effects of tuning their structure and catalytic conditions. To this end, we quantify how modifications to the catalyst fac-Re(4,4′-R-bpy)(CO)3X (bpy = 2,2′-bipyridine, R = OCH3, CH3, tBu, H, CN, CF3; X = Cl, Br, py(OTf), or CH3CN(OTf)) with and without an added proton source (phenol, acetic acid, 2,2,2-trifluoroethanol) affect the catalyst stability, activity, and overpotential. Through cyclic voltammetry experiments, we found that the substituents and proton source had a large effect on both overpotential and activity. Substituents with moderate electron-donating ability (tBu and CH3) increased activity and overpotential in comparison to the unsubstituted complex Re(bpy)(CO)3Cl. In contrast, substituents resulting in too much electron density distributed over the bpy ligand, either from too-strong electron-donating ability (OCH3) or from the requirement of a third reduction to activate the complex (CN and CF3), destabilized the catalyst. An added proton source both increased the activity and decreased the overpotential by 200 mV for all catalyst derivatives, shifting the catalytic mechanism from an electron-first pathway to a proton-first pathway. We used binding energies calculated via density functional theory to help understand the substituent effect on the catalyst affinity for CO2 and other intermediates relevant to the catalytic mechanism. Catalyst activity was quantified using intrinsic rate constants determined through the utilization of catalytic plateau currents, as well as the application of a foot of the wave analysis, which yielded incongruent values. Of those complexes tested, Re(4,4′-tBu-bpy)(CO)3Cl with an added 1 M phenol yielded the most active catalytic system (kcat = 6206 s–1) at an overpotential of 0.67 V.

Kinetic and Mechanistic Effects of Bipyridine (bpy) Substituent, Labile Ligand, and Brønsted Acid on Electrocatalytic CO<sub>2</sub> Reduction by Re(bpy) Complexes

Kinetic and Mechanistic Effects of Bipyridine (bpy) Substituent, Labile Ligand, and Brønsted Acid on Electrocatalytic CO2 Reduction by Re(bpy) Complexes

Kinetic and Mechanistic Effects of Bipyridine (bpy) Substituent, Labile Ligand, and Brønsted Acid on Electrocatalytic CO₂ Reduction by Re(bpy) Complexes