Trispyrazolylborate Ligands Supported on Vinyl Addition Polynorbornenes and Their Copper Derivatives as Recyclable Catalysts

Polynorbornenes prepared by vinyl addition polymerization and bearing pendant alkenyl groups serve as skeletons to support trispyrazolylborate ligands (Tp x ) built at those alkenyl sites. Reaction with CuI in acetonitrile led to VA‐PNB–Tp x Cu(NCMe) (VA‐PBN=vinyl addition polynorbornene) with a 0.8–1.4 mmol incorporation of Cu per gram of polymer. The presence of tetracoordinated copper(I) ions was been assessed by FTIR studies on the corresponding VA‐PNB‐Tp x Cu(CO) adducts, in agreement with those on discrete Tp x Cu(CO). The new materials were employed as heterogeneous catalysts in several carbene‐ and nitrene‐transfer reactions, showing a behavior similar to that of the homogeneous counterparts but also being recycled several times maintaining a high degree of activity and selectivity. This is the first example of supported Tp x ligands onto polymeric supports with catalytic applications.