Trispyrazolylborate Ligands Supported on Vinyl Addition Polynorbornenes and Their Copper Derivatives as Recyclable Catalysts,Chemistry - A European Journal

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Trispyrazolylborate Ligands Supported on Vinyl Addition Polynorbornenes and Their Copper Derivatives as Recyclable Catalysts
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-11-28 , DOI: 10.1002/chem.201803852
Jesús A. Molina de la Torre ₁ , Ignacio Pérez-Ortega ₁ , Álvaro Beltrán ₂ , Manuel R. Rodríguez ₂ , M. Mar Díaz-Requejo ₂ , Pedro J. Pérez ₂ , Ana C. Albéniz ₁

Affiliation

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^xCu(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^xCu(CO) adducts, in agreement with those on discrete Tp^xCu(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.

中文翻译：

乙烯基加成聚降冰片烯及其铜衍生物作为可回收催化剂负载的三吡唑基硼酸酯配体

通过乙烯基加成聚合反应制备并带有链烯基侧基的聚降冰片烯用作骨架，以支撑在这些烯基位点上形成的三吡唑基硼酸酯配体（Tp ^x）。与CuI在乙腈中的反应导致VA-PNB-Tp ^x Cu（NCMe）（VA-PBN =乙烯基加成聚降冰片烯），每克聚合物中Cu的掺入量为0.8-1.4 mmol。通过FTIR研究，在相应的VA-PNB-Tp ^x Cu（CO）加合物上对四配位铜（I）离子的存在进行了评估，与离散Tp ^{x上的一致}铜（CO）。这种新材料在几种卡宾和丁烯转移反应中被用作非均相催化剂，表现出与均相对应物相似的行为，但也多次循环使用，从而保持了较高的活性和选择性。这是通过催化应用将负载的Tp ^x配体负载到聚合物载体上的第一个例子。

更新日期：2018-11-28

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