Highly Active Manganese-Based CO₂ Reduction Catalysts with Bulky NHC Ligands: A Mechanistic Study

Because of the strong σ-donor and weak π-acceptor of the N-heterocyclic carbene (NHC), Mn-NHC complexes were found to be active for the reduction of CO₂ to CO with high activity. However, some NHC-based manganese complexes showed low catalytic activity and required very negative potentials. We report herein that complex fac-[Mn^I(bis-^MesNHC)(CO)₃Br] [1; bis-^MesNHC = 3,3-bis(2,4,6-trimethylphenyl)-(1,1'-diimidazolin-2,2'-diylidene)methane] could catalyze the electrochemical reduction of CO₂ to CO with high activity (TOF_max = 3180 ± 6 s^-1) at a less negative potential. Due to the introduction of the bulky Mes groups, a one-electron-reduced intermediate {[Mn⁰(bis-^MesNHC)(CO)₃]⁰ (2^•)} was isolated as a packed "dimer" and crystallographically characterized. Stopped-flow Fourier-transform infrared spectroscopy was used to prove the direct reaction between doubly reduced intermediate fac-[Mn(bis-^MesNHC)(CO)₃]^- and CO₂; the tetracarbonyl Mn complex [Mn⁺(bis-^MesNHC)(CO)₄]⁺ ([2-CO]⁺) was captured, and its further reduction proposed as the rate-limiting step.