细胞色素P－450单加氧酶的模拟－在锰卟啉催化环己烷加氧反应中不同氧原子供体的作用

Modeling of Cytochrome P-450 Monooxygenase-The Action of Different Single Oxygen Donors During the Oxidation of Cylcohexane Catalyzed by MnTPPCl

以ＭｎＴＰＰＣ１为催化剂研究了不同氧原子供体ＰｈＩＯ、ＮａＯＣｌ和Ｈ２Ｏ２在环己烷加氧反应中的作用。根据动力学考察和ＵＶ－Ｖ１Ｓ、ＩＲ、ＥＳＲ分析认为，ＰｈＩＯ和ＮａＯＣ１可能分别与ＭｎＴＰＰＣ１形成具有转移氧原子能力的单核或双核的高氧化态氧代锰卟啉配合物，而Ｈ２Ｏ２与ＭｎＴＰＰＣ１作用则形成非活性物种。讨论了ＭｎＴＰＰＣ１－单氧原子供体催化环己烷加氧反应机理。

The action of different single oxygen atom donors,such as PhIO,NaOC1,H2O2,during the oxidation of cyclohexane catalyzed by MnTPPC1 were investigated.Based on the kinetic examination and analytic results of UV-Vis,IR,ESR of the intermediates formed by MnThPC1 reacted with different oxidants,it was considered that the high-valent.complexes of mononuclear or dinuclear oxo-Mn porphyrin could be formed when MnTPPC1 reacts with PhIO or NaOC1 respectively,and that these complexes as active species were able to transfer one oxygen atom to the substrate.However an inactive species may be formed when MnTPPC1 reacts with H2O2.The mechanism of oxidation of cyclohexane catalyzed by MnTPPC1 was discussed.