物理化学学报 >> 1999, Vol. 15 >> Issue (08): 715-719.doi: 10.3866/PKU.WHXB19990810

研究论文 上一篇    下一篇

五氟代锰卟啉模拟酶体系快速混合停流吸收谱

李臻, 夏春谷, 尉迟力, 李树本   

  1. 中国科学院兰州化学物理研究所 羟基合成与选择氧化国家重点实验室，兰州 730000
  • 收稿日期:1998-10-05 修回日期:1999-02-02 发布日期:1999-08-15
  • 通讯作者: 夏春谷

Rapid-Mixing Stopped-Flow Spectra of Manganese(Pentafluorophenyl) Porphyrin Enzyme-Mimic Systems

Li Zhen, Xia Chun-Gu, Wei Chi-Li, Li Shu-Ben   

  1. State Key Laboratory for Oxo Synthesis Selective Oxidation,Lanzhou Institute of Chemical Physics,Chinese Academy of Science,Lanzhou 730000
  • Received:1998-10-05 Revised:1999-02-02 Published:1999-08-15
  • Contact: Xia Chun-Gu

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摘要：

采用快速混合停流技术，在实际反应条件下，考察了五氟代锰卟啉配合物ＭｎⅢ（ＴＦＰＰ）Ｃ１与两种单氧给体亚碘酰苯ＰｈＩＯ和过氧苯甲酸ｍ－ＣＰＢＡ构建的细胞色素Ｐ－４５０模拟酶体系催化活性物种的生成及催化烯烃环氧化过程．在氧给体ＰｈＩＯ作用下，ＭｎⅢ（ＴＦＰＰ）Ｃ１生成了高价锰氧卟啉配合物和双核μ－氧锰卟啉配合物，具有高的催化环氧化活性和催化剂稳定性．而在氧给体ｍ－ＣＰＢＡ作用下，ＭｎⅢ（ＴＦＰＰ）Ｃ１则生成了一种较稳定物种，以致催化活性较低.

关键词: 锰卟啉, 单氧给体, 二苯基丁二烯, 环氧化, 停流

Abstract:

The reactions of manganese (pentafluorophenyl) porphrin complex, MnⅢ(TFPP ) C1 with two oxidants iodosobenzene (PhIO) and m-chloroperoxybenzoic acid(m-CPBA) under ambient conditions have been investigated by stopped-flow spectraphotometry. It is shown that high-valent oxomanganese porphyrin complexes and dimeric μ-oxo manganese(IV) porphrin complex intermediates were produced in the reaction between MuⅢ (TFPP)C1 and PhIO, and the oxomanganese porphrin complexes almost completely decomposed to the corresponding MnⅢ（TFPP)C1 species. With m-CPBA as the oxygen donor, only a few short-lived high-valent oxomanganese porpdrin complexes were produced. Epoxidization of 1, 4 - diphenylbutadiene (DPBD) by MnⅢ(TFPP ) C1 with PhIO and m-CPBA showed that since a stable species was produced in the reaction of MuⅢ (TFPP)C1 with m-CPBA, so the reactivity of this model system was lower than that with oxidant PhIO.

Key words: stopped-flow, Manganese porphrin complexes, Iodosobenzene, m-chloroperoxybenzoin cid, Epoxidization