摘要
在温和条件下,在1-辛烯氧化反应中,研究了酞菁铁、钴N-碱加合物的催化作用.发现在室温和0.1MPa的氧气氛中,在共催化剂存在时,酞菁铁、钴N-碱加合物确实具有催化分子氧活化和使其转移至烯烃的功能.酞菁铁N-碱加合物的催化活性总是高于酞菁钴的.同时,在同一中心金属离子的情况下,N-碱配体性质对催化活性有明显影响,其活性序列如下:PcM(pip)_2>PcM(Py)_2>PcM(γ-picol)_2≈PcM(N-MeIm)_2.
The ability of PcTiO2 for transfering oxygen atom in the oxidation of Ph3P and octene-1 was investigated under mild conditions. PcTiO2 can stoichiometrically transfer one oxygen atom to Ph3P in the formation of Ph3PO at room temperature under N2 atmosphere. In the oxidation of octene-1, however, PcTiO2 is quite inert even at 60℃. When cocatalyst, ( PhCN)2PdCl2 was present, PcTiO2 can transfer an oxygen atom to octene-1 in the formation of octanone-2 under N2 atmosphere at 50℃. Visible and IR spectra results showed that(PhCN)2 PdCl2 may serve as an activator for olefin in the oxidation of olefin. At the, same time, experiments indicated that, PcTiO2 may play a role for reoxidizing Pd0 in the oxidation of octene-1 by PcTiO2 in the presence of ( PhCN)2 PdCl2. Experimental results using molecular oxygen as an oxidant showed that in the above mentioned two reactions, PcTiO2 cannot form a catalytic oxidation system, it can only serve as a stoi-chiometric reagent for transforing one oxygen atom during the oxidation of Ph3P and octene-1. The process of oxygen atom transfer was discussed briefly.
出处
《分子催化》
EI
CAS
CSCD
1989年第4期284-291,共8页
Journal of Molecular Catalysis(China)
基金
国家自然科学基金支持项目
