Influence of phosphite ligands concentration on 1-butene hydroformylation over Rh-supported porous organic polymer catalysts

A series of porous organic polymer with different concentrations of tri(4-vinylphenyl)phosphite (P(OPh) 3 ) moieties were synthesized through the solvothermal synthesis technique. Their performance were investigated in 1-butene hydroformylation after metalation with metal species. The effect of the concentration of P(OPh) 3 moieties and pore structure of the polymers on catalytic efficiency were investigated in detail. The polymer-based Rh catalysts demonstrated a decrease in catalytic activity and inverse trends in selectivity with the increasing concentration of P(OPh) 3 . More importantly, Rh/POP-PhPh 3 -BP-P(OPh) 3 -x catalysts containing biphephos moieties exhibited more excellent catalytic performance than the corresponding Rh/POP-PhPh 3 -P(OPh) 3 -x catalysts. And the optimal catalytic performance, a valeraldehyde n/i ratio of 60.4, a valeraldehyde TOF of 9589.9 h −1 , and good catalytic stability were acquired for Rh/POP-PhPh 3 -BP-P(OPh) 3 –0.9 catalyst. The extraordinary catalytic properties are attributed to the formation of abundant active pentacoordinated hydridorhodium complexes, as demonstrated by in situ FT-IR experiments.