Cooperative Catalytic Activation of Si−H Bonds: CO2‐Based Synthesis of Formamides from Amines and Hydrosilanes under Mild Conditions

A simple cooperative catalytic system was successfully developed for the solvent-free N-formylation of amines with CO₂ and hydrosilanes under ambient conditions, which was composed of a Zn(salen) catalyst and quaternary ammonium salt. These commercially available binary components activated the Si-H bonds effectively, owing to the intermolecular synergistic effect between Lewis base and transition metal center (LB-TM), and subsequently facilitated the insertion of CO₂ to form the active silyl formats, thereby leading to excellent catalytic performance at a low catalyst loading. Furthermore, the bifunctional Zn(salen) complexes, with two imidazolium-based ionic-liquid (IL) units at the 3,3'-position of salen ligand, acted as intramolecularly cooperative catalysts, and the solvent-regulated separation resulted in facile catalyst recycling and reuse.