Development of Metal Cluster Catalysts Supported on Porous Chelate Resins

1.金属簇合物在螯合树脂上的固定化将六氯铂离子固定在含有亚氨基二乙酸基的交联聚苯乙烯的铝络合物上，然后用硼化锂连续还原铂(IV)离子，得到了树脂负载铂簇合物催化剂。钠(I)和镁(II)是通过与铝(III)离子交换得到的。采用硼氢化锂负载钯(II)离子的方法制备了螯合树脂负载的钯簇合物催化剂。螯合树脂络合物负载金属络合物的表征络合树脂络合物和含金属簇合物的络合树脂络合物的比表面积随着金属离子价态的增加而增大。络合树脂的Al(III)络合物大部分直径为40A，而铂簇合物的平均直径为26A，表明簇合物粒子占据了孔隙。树脂中的金属离子也会影响团簇的分布。络合树脂负载金属簇合物的催化作用所得到的铂、钯簇合物在温和的条件下对烯烃和二烯的加氢反应具有良好的催化活性。催化剂的催化活性随树脂比表面积的增大而增大。加氢速率还取决于底物-载体的相互作用和载体中团簇的分布。

1. Immobilization of Metal Clusters on Chelate ResinImmobilization of hexachloroplatinate ions on the aluminum complex of the chelate resin, crosslinked polystyrene containing iminodiacetic acid moieties, and then successive reduction of the platinum (IV) ions by lithium borotydride gave the resin-supported platinum cluster catalyst. Sodium (I) and magnesium (II) derevatives were obtained by ion exchange with aluminum (III). The chelate resin complex-supported palladium cluster catalysts were prerared by immobilization of palladium (II) ions with lithium borohydride.2. Characterization of Chelate Resin Complex-Supported Metal ClusrersThe surface area of the chelate resin complex as well as the metal cluster-containing chelate resin complex increases with the valency of the metal ion involved. Most of the porse of the Al (III) complex of the chelate resin are 40 A in diameter, while the platinum cluster has the average diameter of 26 A, which suggests the cluster particles occupy the pores. The metal ion involved in the resin can affect the distribution of clusters, too.3. Catalyses of Chelate Resin Complex-Supported Metal ClustersThe platinum and palladium clusters thus obtained are active as the catalysts for hydrogenation of olefin and diene under mild conditions. The catalytic activity increases with increase of the surface area of the resin. The hydrogenation rate also depends both on the substrate-support interaction and on the distribution of the clusters in the support.