Schiller Alexander, Scopelliti Rosario, Severin Kay
Institut des Sciences et Ingénieries Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Dalton Trans. 2006 Aug 28(32):3858-67. doi: 10.1039/b605676h. Epub 2006 Jul 10.
The chelate ligand tris[(1-vinylimidazol-2-yl)methyl]amine (5) was synthesized in five steps from commercially available starting materials. Upon reaction with ZnCl2 or CuCl2 in the presence of NH4PF6, the complexes [Zn5Cl]PF6 (6) and [Cu5Cl]PF6 (7) were obtained. The structure of both complexes was determined by single-crystal X-ray crystallography. Immobilization of 6 and 7 was achieved by co-polymerization with ethylene glycol dimethacrylate. The supported complexes P6-Zn and P7-Cu were found to be efficient catalysts for the hydrolysis of bis(p-nitrophenyl)phosphate (BNPP) at 50 degrees C. At pH 9.5, the heterogeneous catalyst P7-Cu was 56 times more active than the homogeneous catalyst 7. Partitioning effects, which increase the local concentration of BNPP in the polymer, are shown to contribute to the enhanced activity of the immobilized catalyst.
螯合配体三[(1-乙烯基咪唑-2-基)甲基]胺(5)由市售起始原料经五步合成。在NH4PF6存在下与ZnCl2或CuCl2反应，得到配合物[Zn5Cl]PF6(6)和[Cu5Cl]PF6(7)。通过单晶X射线晶体学确定了两种配合物的结构。通过与乙二醇二甲基丙烯酸酯共聚实现了6和7的固定化。发现负载型配合物P6-Zn和P7-Cu在50℃下是双(对硝基苯基)磷酸酯(BNPP)水解的有效催化剂。在pH 9.5时，多相催化剂P7-Cu的活性比均相催化剂7高56倍。聚合物中BNPP局部浓度增加的分配效应被证明有助于固定化催化剂活性的提高。
