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 CO 2 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 CO 2 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.