Acta Chimica Sinica ›› 2001, Vol. 59 ›› Issue (3): 371-376. Previous Articles     Next Articles

Original Articles

水溶性锰卟啉体系催化氧化反应停流谱研究

李臻;夏春谷   

  1. 中国科学院兰州化学物理研究所.兰州(730000);中国科学院羰基合成与选择氧 化国家重点实验室
  • 发布日期:2001-03-15

Sopped-flow spectra studies on oxidation catalyzed by water-soluble manganese porphyrin systems

Li Zhen;Xia Chungu   

  1. Lanzhou Inst Chem Phys, CAS.Lanzhou(730000)
  • Published:2001-03-15

The reaction of water-soluble manganese porphyrin complex, Mn^I^I^I (TMPyP), with two oxidants (NaOCl and KHSO~5) in 1:1 (V/V) CH~3CN/H~2O at pH 7.4 was investigated using the stopped-flow technique. In this reaction system, high-valent oxo-manganese(V) porphyrin (1) and oxo manganese (IV) porphyrin (2) were produced. Epoxidation of trans, trans-1, 4-diphenyl-1, 3-butadiene (DPBD) by Mn^I^I^I(TMPyP) with NaOCl and KHSO~5 showed that reactivity of the Mn^I^I^I(TMPyP)-KHSO~5 model system was higher than that of the Mn^I^I^I(TMPyP)-NaOCl system. In the Mn^I^I^I(TMPyP)-KHSO~5 model system, intermediate 2 was also active. The mechanism of oxygen atom transfer from the high-valent manganese prophyrine to olefine is discussed.

Key words: MANGANESE COMPLEX, PORPHYRIN, CATALYTIC OXIDATION, STOPPED-FLOW TECHNIQUE, CATALYTIC ACTIVITY

CLC Number: