Confinement of atomically dispersed Rh catalysts within porous monophosphine polymers for regioselective hydroformylation of alkenes

Precisely controlling the regioselectivity with monophosphine ligand is a long-standing challenge in hydroformylation. Herein, we describe the one-pot encapsulation of single-atom Rh catalysts within porous monophosphine polymers for regioselective heterogeneous hydroformylation of alkenes. The optimized catalyst ([email protected]) shows remarkable enhancement of regioselectivity compared with the combination of Rh(CO)2(acac) and monophosphine ligand (PTBA), and the linear aldehyde selectivity increases from 62% to 92%. In addition, this catalyst shows excellent catalytic activity (one run TON at least 60,000) and good stability. Detailed studies reveal that the encapsulation of atomically dispersed Rh catalysts within porous monophosphine polymers may endow the catalysts with high regioselectivity, while the encirclement of metal active species by abundant but dispersive phosphine ligand would strengthen the stability of the catalysts through multiple-sites-coordination. The present study provides meaningful insights for designing heterogeneous catalysts with good regioselectivity, and merging the advantages of homogeneous and heterogeneous catalysis.