Highly Efficient Thiolate‐Based Ionic Liquid Catalysts for Reduction of CO2: Selective N‐Functionalization of Amines to Form N‐Formamides and N‐Methylamines

Abstract Developing efficient catalysts to convert CO2 into value‐added chemicals is valuable for reducing carbon emissions. Herein, a kind of novel thiolate‐based ionic liquid with sulfur as the active site was designed and synthesized, which served as highly efficient catalyst for the reductive N‐functionalization of CO2 by amines and hydrosilane. By adjusting the CO2 pressure, various N‐formamides and N‐methylamines were selectively obtained in high yields. Remarkably, at the catalyst loading of 0.1 mol %, the N‐formylation reaction of N‐methylaniline exhibited an impressive turnover frequency (TOF) up to 600 h−1, which could be attributed to the roles of the ionic liquids in activating hydrosilane and amine. In addition, control experiments and NMR monitoring experiments provided evidence that the reduction of CO2 by hydrosilane yielded formoxysilane intermediates that subsequently reacted with amines to form N‐formylated products. Alternatively, the formoxysilane intermediates could further react with hydrosilane and amine to produce 4‐electron‐reduced aminal products. These aminal products served as crucial intermediates in the N‐methylation reactions.