Schätz Alexander, Long Toby R, Grass Robert N, Stark Wendelin J, Hanson Paul R, Reiser Oliver
Institute for Organic Chemistry, University of Regensburg, Universitätsstr. 31, D-93053 Regensburg, Germany.
Adv Funct Mater. 2010 Dec 21;20(24):4323-4328. doi: 10.1002/adfm.201000959.
A novel hybrid material is reported as support for a recyclable palladium catalyst via surface immobilization of a ligand onto Co-based magnetic nanoparticles (NPs). A standard "click" reaction is utilized to covalently attach a norbornene tag (Nb-tag) to the surface of the carbon coated cobalt NPs. The hybrid magnetic nanoparticles are produced by initiating polymerization of a mixture containing both Nb-tagged ligand (Nb-tagged PPh (3)) and Nb-tagged carbon coated cobalt NPs. In turn, the norbornene units are suitably functionalized to serve as ligands for metal catalysts. A composite material is thus obtained which furnishes a loading that is one order of magnitude higher than the value obtained previously for the synthesis of functionalized Co/C-nanopowders. This allows for its application as a hybrid support with high local catalyst concentrations, as demonstrated for the immobilization of a highly active and recyclable palladium complex for Suzuki-Miyaura cross-coupling reactions. Due to the explicit magnetic moment of the cobalt- NPs, the overall magnetization of this organic/inorganic framework is significantly higher than of polymer coated iron oxide nanoparticles with comparable metal content, hence, its rapid separation from the reaction mixture and recycling via an external magnetic field is not hampered by the functionalized polymer shell.
据报道,一种新型杂化材料可通过将配体表面固定在钴基磁性纳米颗粒(NPs)上,作为可回收钯催化剂的载体。利用标准的“点击”反应将降冰片烯标签(Nb标签)共价连接到碳包覆钴纳米颗粒的表面。通过引发含有Nb标签配体(Nb标签PPh(3))和Nb标签碳包覆钴纳米颗粒的混合物的聚合反应,制备了杂化磁性纳米颗粒。反过来,降冰片烯单元经过适当功能化,用作金属催化剂的配体。由此获得的复合材料的负载量比先前合成功能化Co/C纳米粉末所获得的值高一个数量级。这使得它能够作为具有高局部催化剂浓度的杂化载体应用,如用于固定用于铃木-宫浦交叉偶联反应的高活性和可回收钯配合物所证明的那样。由于钴纳米颗粒具有明显的磁矩,这种有机/无机框架的总磁化强度明显高于具有可比金属含量的聚合物包覆氧化铁纳米颗粒,因此,其从反应混合物中的快速分离以及通过外部磁场的回收不会受到功能化聚合物壳的阻碍。