Catal. Today, 2017, 298, 40-45.

Enhancementof hydroformylation performance via increasing the phosphineligand concentration in porous organic polymer catalysts.

The development of highly efficientand stable Rh-based heterogeneous catalysts for hydroformylation ofheavier olefins is of both high fundamental and industrial interest, yet therestill remains a tremendous challenge. In this contribution, a series of porousorganic polymers bearing various concentrations of triphenylphosphine (PPh3) moieties, a ligand of industrialchoice, was synthesized and their performance in the hydroformylation ofstyrene, 1-ocetene, and 2-ocetene were investigated after metalation with Rhspecies. Both concentration of PPh3 moietiesand pore structure of the polymers were found to influence the catalyticperformance. The polymer-based rhodium catalysts demonstrated an increase incatalytic activity, selectivity, and stability when the concentration of PPh3 was increased and the porouspolymer constructed by the functional PPh3 monomer(POL-PPh3) wasfound to be optimal among all the solid ligands tested. We anticipate theseresults will form the basis for a constructive perspective in the developmentof high performance heterogeneous Rh-based hydroformylationcatalysts. Moreover, our observations indicate the considerable potential ofporous organic polymers (POPs) as a new generation of heterogeneous catalyticplatforms that may prove effective when targeting important but highlychallenging reactions.