金属离子在液相氧化中的催化作用——Ⅹ.过渡金属氯化物与简单配体原位形成的配合物在环己烯氧化反应中的催化作用

本文研究了由过渡金属氯化物(MnCl_2、FeCl_2、CoCl_2、CuCl)与2,2′-二吡啶原位形成的配合物,在环己烯氧化反应中的催化性能以及配体性质对所形成的配合物催化性能的影响.结果表明,多种过渡金属氯化物可与2,2′-二吡啶原位形成有催化活性的配合物,其催化活性与金属离子性质、形成配合物能力以及配体性质有关.

CATALYTIC ACTION OF METAL IONS IN THE LIQUID PHASE OXIDATION X.CATALYTIC ACTION OF TRANSITION METAL CHLORIDES WITH 2,2'-BIPYRIDINE IN THE OXIDATION OF CYCLOHEXENE

The catalytic action of transition metal chlorides (MnCl2, FcCl2, CoCl2, CuCl) with 2,2'-bipyridine in the liquid phase oxidation of cyclohexcnc was investigated. It was found that the catalytic activity, the induction period, the product distribution and the electronic spectra of catalyst system (MClx / bipyridc) were similar with that of the corresponding synthetic complexes M(bipy)n. The experimental result clearly indicated that transition metal chlorides can react with bipyride during the reaction and form a complex in situ which have catalytic activity for the oxidation of cyclohcxcne. The experimental result concerning the effect of various ligands on the catalytic activity showed that the catalytic activity of complex formed in situ relates with the basicity of ligands, and that the catalytic system consisted of mixed ligands (bipy with py or pip) is more active than that of catalytic system with single ligand (bipy or py or pip).