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以 [Fe2 Dhist(OAc) 2 ]BPh4·3H2 O为模型配合物、Zn粉为电子给体、HOAc为质子给体、甲基紫精 (MV2 +)为电子传递剂作为甲烷单加氧酶 (MMO)模拟体系在室温下实现了分子氧的还原活化和烃类的分子氧氧化 ,并用电子顺磁共振 (EPR)研究了分子氧的络合和活化过程 .结果表明 ,苯乙烯主要生成环氧苯乙烷 ( 1 396mol/1 0 0molFe2 配合物 )、苯甲醛 ( 1 6 1 6 0 )和苯乙酮 ( 986 ) ;环己烷生成环己醇 ( 9370 )和环己酮 ( 2 6 70 ) .FeⅣFeⅣ O是反应的活性中间体 ,由FeⅢFeⅢ 经还原、载氧、质子化形成 ,并与CC或C—H作用分别得到各氧化产物 .反应现象、EPR研究和产物分布与蚯蚓血红蛋白、MMO的有关过程十分相似 ,是一个良好的MMO模型体系 .相应的Mn2 ,FeZn及单Fe核配合物无活性 ,表明Fe2 核对产生催化活性是必需的 .
Using [Fe2 Dhist (OAc) 2] BPh4 · 3H2O as a model complex, Zn powder is an electron donor, HOAc is a proton donor, methyl viologen (MV2 +) is an electron transfer agent as methane monooxygenase MMO) system was used to carry out the reduction and activation of molecular oxygen and the molecular oxygen oxidation of hydrocarbons at room temperature, and the complexation and activation process of molecular oxygen were studied by electron paramagnetic resonance (EPR). The results showed that styrene mainly generated epoxy (1 396 mol / 100 mol Fe2 complex), benzaldehyde (1 6 1 6 0) and acetophenone (986); cyclohexane to cyclohexanol (9370) and cyclohexanone .FeⅣFeⅣ O is the active intermediate of the reaction, which is formed by the reduction, oxygenation and protonation of Fe Ⅲ Fe Ⅲ, and the oxidation products are obtained respectively by interaction with CC or C-H. The reaction phenomenon, EPR study and product distribution are similar to those of earthworm hemoglobin, MMO The process is very similar and is a good MMO model system.The corresponding Mn2, FeZn and single Fe core complexes are inactive, indicating that the Fe2 nucleation is necessary to produce catalytic activity.