Acta Chimica Sinica ›› 1999, Vol. 57 ›› Issue (4): 415-422. Previous Articles     Next Articles

Original Articles

甲烷单加氧酶的化学模拟: 酚氧双羧酸根桥联Fe~2(III)和 Mn~2(III)配合物合 成、表征及催化性能

魏俊发;何地平;俞贤达;金道森   

  1. 陕西师范大学化学系.西安(710062);中国科学院兰州化学物理研究所.兰州 (730000)
  • 出版日期:1999-04-15 发布日期:1999-04-15

Model systems for methane monooxygenase: Synthesis, characterization and catalytic property of (μ-phenoxo)bis( μ-carboxylato) dimetal [Fe(III), Mn(III)] complexes

Wei Junfa;He Diping;Yu Xianda;Jin Daosen   

  1. Shanxi Normal Univ, Dept Chem.Xian(710062);Lanzhou Inst Chem Phys, CAS.Lanzhou(730000)
  • Online:1999-04-15 Published:1999-04-15

A methane monooxygenase (MMO)-like dinuclear metal (iron/manganese) complex which consists of a [(μ -phenoxo)bis(μ-carboxylato)dimetal] core and a chiral phenolic ligand bearing two chelating arms of L- histidine has been synthesized and characterized. Its catalytic properties in olefin epoxidations and in alkane hydroxylations were investigated with iodosylbenzene as a therminal oxidant. It has been found that the Fe~2 complex nicely reproduces some qualititive characteristics of electronic spectrum of MMO. It is able to catalyze the epoxidation of styrene giving styrene oxide in a 840% yield (based on the catalyst) and a 45.4% e.e. for the R-(+)-enantiomer. Similarly, using the Mn~2 analogue complex, styrene gave corresponding epoxide in a 7080% yield and a 51.6% e.e. for the R- enantiomer and cyclohexene gave epoxycyclohexane (3880%) as a major product together with cyclohexenol (603%) and cyclohexenone (189%). In addition, the Mn~2 complex catalyzed the hydroxylation of cyclohexane giving cyclohexanol (1053%) and cyclohexanone (639%). EPR evidence suggested the presence of a high valent metal-oxo intermediate in the reactions.

Key words: IRON COMPLEX, MANGANESE COMPLEX, CATALYTIC BEHAVIOUR, BENZENE P, ALKENE, EPOXIDATION REACTION

CLC Number: