Computational study for CO₂-to-CO conversion over proton reduction using [Re[BpyMe(Im-R)](CO)₃Cl]⁺ (R = Me, Me₂, and Me₄) electrocatalysts and comparison with manganese analogues

The Nippe group has previously reported a series of imidazolium-functionalized rhenium bipyridyl tricarbonyl electrocatalysts, [Re[bpyMe(Im-R)](CO)₃Cl]⁺ (R = Me and Me₂), for CO₂-to-CO conversion using H₂O as the proton source [Sung, S.; Kumar, D., et al. Electrocatalytic CO₂ Reduction by Imidazolium-Functionalized Molecular Catalysts. J. Am. Chem. Soc. 2017, 139, 40, 13993−13996. 10.1021/jacs.7b07709]. These compounds feature charged imidazolium ligands in the secondary coordination sphere and exhibit higher catalytic activities as compared to the Lehn catalyst [Re(bpy)(CO)₃Cl] (where bpy = 2,2'-bipyridine). However, the reaction mechanism for the CO₂ reduction reaction (CO₂RR) over the competing hydrogen evolution reaction (HER) is unclear. Here, we employ density functional theory (DFT) and restricted active space self-consistent field (RASSCF) methods to study the selectivity for CO₂ fixation using [Re[bpyMe(ImMe)](CO)₃Cl]⁺ (1⁺) in water and compare its reactivity to [Re[bpyMe(ImMe₂)](CO)₃Cl]⁺ (2⁺) and [Re[bpyMe(ImMe₄)](CO)₃Cl]⁺ (3⁺). Our results reveal that the turnover frequency (TOF) for CO₂RR using 1⁺ is 4 orders of magnitude higher than for proton reduction, consistent with controlled potential electrolysis (CPE) experiments in which CO was the only detectable reduction product. The imidazolium moiety in the secondary coordination sphere stabilizes the metallocarboxylate species and assists the C−O cleavage through intermolecular hydrogen-bonding stabilizations. Furthermore, our calculations imply that the strongest hydrogen-bonding interactions at the C2 position in 1⁺ contribute to the faster reaction rate observed experimentally with respect to 2⁺. More significantly, the use of the energy span model demonstrates that the turnover frequency-determining transition state (TDTS) corresponds to the formation of the Re−CO₂ adduct, contrasting with manganese analogues in which the C−O bond cleavage step is the TDTS. We attribute this distinction based on the electronic structures of doubly reduced active catalysts. Indeed, RASSCF calculations indicate that rhenium compounds are best described as a rhenium(I) coupled with a doubly reduced bipyridine ligand, [Re^I[bpyMe(ImMe)²⁻](CO)₃]⁰.