Cooperativity Between Porosity and Phosphorus Content in Polyphosphamides for Improving Catalytic Appel Reactions

Although phosphamide‐based organic polymers (POPs) are promising flame‐retardant materials, they can also act as promising heterogeneous catalysts due to the presence of redox‐acitve –NH–P(O) unit. Recently, POPs have been used as catalysts for photochemical, electrochemical CO 2 reduction or CO 2 utilization, and water‐splitting reactions. Herein, a nitrogen‐rich mesoporous POP is synthesized via covalently linking the –NH–P(O) moiety to a pyridine ring. In this study, POP with a BET surface area of 22 m 2 g −1 with a phosphorus content of 15.1%, is explored for the catalytic Appel reaction with a highest TON of 696. Here, POP is compared with two analogous polyphosphamides, PPA (nonporous) and p‐PPA (porous). PPA with a phosphorus content of 19.7% shows a lower TON of 462. p‐PPA with a BET surface area between 1.773 m 2 g −1 and 17.1% of phosphorus resulted in a TON of 561. The better catalytic performance of POP could be ascribed to an increase in the BET surface area. A wide range of substrate scope is achieved for both bromo and chloro Appel products. Post‐characterization data after five consecutive cycles confirm the sustainability of POP. The cooperative action of redox‐active phosphorus‐center and high‐porosity of POP lead superior catalytic activity.