Hydrogenation of CO₂ to MeOH Catalyzed by Highly Robust (PNNP)Ir Complexes Activated by Alkali Bases in Alcohol

Despite receiving significant attention, well-defined homogeneous complexes for hydrogenation of carbon dioxide (CO2) to methanol (MeOH) are scarce and suffer issues of low catalyst turnover numbers (TONs) at high catalyst concentrations and deactivation in the presence of CO and at elevated temperatures. Herein, we disclose a system deploying sterically demanded (PNNP)Ir complexes for a sustained activity for hydrogenation of CO2 to MeOH at temperatures ∼200 °C in an alcohol solvent. Through reaction optimization, we achieved a TON of ∼9000 for MeOH formation, which exceeds most active homogeneous systems reported to date, and robustness on par with or exceeding most reactive systems utilizing amine additives was demonstrated. The key to achieving sustained catalyst turnover for the system was utilizing a catalytic amount of an alkali base additive, which serves the dual purpose of facilitating more efficient outer-sphere reduction of CO2 and HCO2Et and enhancing the selectivity of MeOH over in situ formed CO.