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Trispyrazolylborate Ligands Supported on Vinyl Addition Polynorbornenes and Their Copper Derivatives as Recyclable
Jesús A Molina de la Torre1, Ignacio Pérez-Ortega1, Álvaro Beltrán2
1IU CINQUIMA/Química Inorgánica, Universidad de Valladolid, 47071, Valladolid, Spain.
Abstract:
Polynorbornenes prepared by vinyl addition polymerization and bearing pendant alkenyl groups serve as skeletons to support trispyrazolylborate ligands (Tpx ) built at those alkenyl sites. Reaction with CuI in acetonitrile led to VA-PNB-Tpx 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-Tpx Cu(CO) adducts, in agreement with those on discrete Tpx 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 Tpx ligands onto polymeric supports with catalytic applications.
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