The valorization of carbon dioxide (CO₂) to fine chemicals is one of the most promising approaches for CO₂ 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 CO₂ adsorption capability are crucial to achieve excellent selectivity and yields towards N-formylation of diverse amines with CO₂ and H₂ 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 × 10⁶) 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.

   https://onlinelibrary.wiley.com/doi/10.1002/anie.202011260