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化学学报
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化学学报 ›› 2001, Vol. 59 ›› Issue (3): 371-376. 上一篇    下一篇

研究论文

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

PDF

346

被引次数

4

采用快速混合停流技术，考察了pH=7.4，V(CH~3CN):V(H~2O)=1:1的混合溶剂中水溶性锰卟啉Mn^I^I^I(TMPyP)与单氧给体NaOCl及KHSO~5构建的细胞色素P-450模拟酶体系催化氧化活性物种的生成及催化烯烃DPBD环氧化过程。实验表明，在反应进行中存在着两种中间体：oxo-Mn^V(Por.)(1)和oxo-Mn^I^V(Por.)(2)，但两者的催化活性有差异，在催化烯烃DPBD环氧化反应中，对于Mn^I^I^I(TMPyP)-NaOCl体系起催化作用的主要作用的主要是中间体1，而对于Mn^I^I^I(TNPyP)-KHSO~5体系两种中间体均与烯烃配位生成环氧化产物，并且该体系催化活性较高。

关键词: 锰络合物, 卟啉, 催化氧化, 停流技术, 催化活性

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

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