Catalytic Hydrogenation of Carbon Dioxide with Ammonia–Borane by Pincer-Type Phosphorus Compounds: Theoretical Prediction

Two theoretically designed and one experimentally reported pincer-type phosphorus compounds are found to be active for the hydrogenation of carbon dioxide with ammonia–borane. DFT, ONIOM­(CCSD­(T):MP2), and CCSD­(T) computational results demonstrated that the reaction occurs through phosphorus–ligand cooperative catalysis, which provides an unprecedented protocol for metal-free CO₂ conversion. The phosphorus compounds with the NNN ligand are more active than those with the ONO ligand. The planar conjugate ligand considerably improves the efficiency of the catalyst