Highly Efficient and Selective N‐Formylation of Amines with CO2 and H2 Catalyzed by Porous Organometallic Polymers

Abstract The valorization of carbon dioxide (CO 2 ) to fine chemicals is one of the most promising approaches for CO 2 capture and utilization. Herein we demonstrated a series of porous organometallic polymers could be employed as highly efficient and recyclable catalysts for this purpose. Synergetic effects of specific surface area, iridium content, and CO 2 adsorption capability are crucial to achieve excellent selectivity and yields towards N‐formylation of diverse amines with CO 2 and H 2 under mild reaction conditions even at 20 ppm catalyst loading. Density functional theory calculations revealed not only a redox‐neutral catalytic pathway but also a new plausible mechanism with the incorporation of the key intermediate formic acid via a proton‐relay process. Remarkably, a record turnover number (TON=1.58×10 6 ) was achieved in the synthesis of N,N‐dimethylformamide (DMF), and the solid catalysts can be reused up to 12 runs, highlighting their practical potential in industry.