摘要
本文研究了过氧酞菁钛(PcTi0_2)在三苯基膦(Ph_3P)以及1-辛烯氧化反应中氧原子转移性能.在温和条件下,PcTiO_2可化学计量地转移一个氧原子至Ph_3P形成Ph_3O.然而,在1-辛烯的氧化反应中,只有在共催化剂,(PhCN)_2PdCl_2存在下,PcTiO_2才能将氧原子转移至被Pd化合物活化的烯烃上形成辛酮.实验结果表明,PcTiO_2在上述两个氧化反应中,只能起转移一个氧原子的作用,不可能形成以分子氧为氧化剂的催化氧化体系.
The catalytic action of N-base adducts of phthalocyaninatoiron and cobalt under mild conditions was investigated. It was found that, in the presence of cocatalyst, ( PhCN ) 2PdCl2, the N-base adducts of phthalocyninatoiron and cobalt posses the function of catalytic activation and transfer of molecular oxygen to octene-1 to form octanone-2 at room temperature and under 1atm pressure of oxygen. The catalytic activity of PcFe(N-B)2 is always higher than that of PcCo ( N-B ) 2 under the same experimental conditions. At the same time, for the same metal ion in phthalocyanine complex, the nature of N-base ligand influnces the catalytic activity of N-base adducts of phtha-locynine complexes in the following order: PcM ( pip ) 2>PcM ( Py )2> PcM(γ-picol)2≌PcM(N-MeIm)2. The IR spectral results of PcFe(N-B)2 after the reaction show that μ-oxo PcFe(N-B)2 may be formed at the, end of reaction. Therefore, an intermediate active complex for oxygen atom transfer must be involved in the oxidation of octene by PcFe (N-B)2 with molecular oxygen.
出处
《分子催化》
EI
CAS
CSCD
1989年第4期292-296,共5页
Journal of Molecular Catalysis(China)
基金
国家自然科学基金支持项目
