Methane Generation from CO₂ with a Molecular Rhenium Catalyst

The atomic-level tunability of molecular structures is a compelling reason to develop homogeneous catalysts for challenging reactions such as the electrochemical reduction of carbon dioxide to valuable C₁-C products. Of particular interest is methane, the largest component of natural gas. Herein, we report a series of three isomeric rhenium tricarbonyl complexes coordinated by the asymmetric diimine ligands 2-(isoquinolin-1-yl)-4,5-dihydrooxazole (quin-1-oxa), 2-(quinolin-2-yl)-4,5-dihydrooxazole (quin-2-oxa), and 2-(isoquinolin-3-yl)-4,5-dihydrooxazole (quin-3-oxa) that catalyze the reduction of CO₂ to carbon monoxide and methane, albeit the latter with a low efficiency. To our knowledge, these complexes are the first examples of rhenium(I) catalysts capable of converting carbon dioxide into methane. Re(quin-1-oxa)(CO)₃Cl (1), Re(quin-2-oxa)(CO)₃Cl (2), and Re(quin-3-oxa)(CO)₃Cl (3) were characterized and studied using a variety of electrochemical and spectroscopic techniques. In bulk electrolysis experiments, the three complexes reduce CO₂ to CO and CH₄. When the controlled-potential electrolysis experiments are performed at -2.5 V (vs Fc^+/0) and in the presence of the Brønsted acid 2,2,2-trifluoroethanol, methane is produced with turnover numbers that range from 1.3 to 1.8. Isotope labeling experiments using ¹³CO₂ atmosphere produce ¹³CH₄ (m/z = 17) confirming that methane originates from CO₂ reduction. Theoretical calculations are performed to investigate the mechanistic aspects of the 8e^-/8H⁺ reduction of CO₂ to CH₄. A ligand-assisted pathway is proposed to be an efficient pathway in the formation of CH₄. Delocalization of the electron density on the (iso)quinoline moiety upon reduction stabilizes the key carbonyl intermediate leading to additional reactivity of this ligand. These results should aid the development of more robust catalytic systems that produce CH₄ from CO₂.