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Abstract
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-PhPh3-BP-P(OPh)3-x catalysts containing biphephos moieties exhibited more excellent catalytic performance than the corresponding Rh/POP-PhPh3-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-PhPh3-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.
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