摘要
考察了碱性介质下分子氧对醇类的氧化反应中双齿铜(Ⅱ)络合物的催化性能。对氧化反应的溶剂选择和溶剂效应,碱性和碱的作用机制,络合物的配位体影响等作了实验考察和理论探讨。提出了铜(Ⅱ)络合物的可解离性和柔曲性(可形变性)与催化性能的相互关系。
Binary copper (Ⅱ) complexes Cu(ACAC)2, Cu(PIC)2, Cu[ ( DEPIC)]2 (ClO4)2, Cu (GLY)2[Cu (BIPY)2](C1O4)2, [Cu(BIPY)3](ClO4)2 and ternary copper(Ⅱ)complexes Cu(BIPY)Cl2, [Cu(BIPY) (H2O)2] (C1O4)2, [Cu(BIPY)(SALDE)]C1O4, [Cu(BIPY)(ACAC)]ClO4, [Cu(BIPY)(PIC)] C1O4 were found to be effective catalysts for the oxidation of aromatic and aliphatic alcohols. Primary and secondary alcohols are oxidized to the corresponding aldehydes and ketones, and dioxygen is reduced to water in DMF solvent containing NaOH at room temperature. The selection of solvents and effects of the solvent on the reaction have been investigated. The results show that the rate of oxidation reaction in DMF solvent is remarkably higher than those in other solvents.
The important role of solvents in the catalytic oxidation was discussed. Influence of ligands on the oxidation was studied also. It was indicated that the dissociation ability and the flexibility of copper(Ⅱ ) complexes were two important factors in this catalytic reaction. The catalytic activity of bidentate complexes is higher than that of tet-radentate complexes. The former can bring about the oxidation reaction without DMF solvent. Its catalytic activity was also related to the type and strength of the bonds between metal ion and ligands. The effects of alkaline were studied. It was found that the catalytic reaction is inhibited by water.
出处
《分子催化》
EI
CAS
CSCD
1991年第4期316-324,共9页
Journal of Molecular Catalysis(China)
基金
国家自然科学基金
