Turning on Catalysis: Construction of Triphenylphosphine Moieties into Porous Frameworks

Abstract In this work, we present an effective strategy to enhance the reactivity and durability of molecular organometallic catalysts by constructing into porous frameworks, as demonstrated by triphenylphosphine (PPh 3 ). Such PPh 3 moieties accessible via the porous structures could be partially metalated by Pd species to generate a highly efficient and recyclable heterogeneous catalyst for the Suzuki coupling of aryl chlorides. Site isolation in the rigid framework stabilizes the catalytically active monophosphine‐ligated complex against deactivation into less active assemblies of bisphosphine‐Pd. Meanwhile, the densely populated free ligands inhibit the decomposition of catalytically active sites thereby highlighting the beneficial effects of such a platform. Thus, the tunability of porous polymer synthesis gives great promise to impart numerous organometallic catalysts constituted by readily available ligands with unique reactivity, which are not trivially achievable with traditional systems.