金属卟啉催化下环己烷羟基化反应中的Hammett关系

合成了40个卟啉环上具有不同取代基的单铁、锰卟啉和u-氧桥连双铁、锰卟啉,研究了这些金属卟啉模拟细胞色素P－450单充氧酶在温和条件下催化环己烷羟基化的反应.首次用线性自由能关系对金属卟啉仿生催化反应和金属卟啉自氧化反应进行相关分析,获得一些新的结果和规律.在此基础上,对金属卟啉仿生催化反应的可能机理进行了探讨.

Hammett Relationship in Cyclohexane Hydroxylation Catalyzed by Metalloporphyrins

Forty mono-iron and manganese porphyrins, u-oxo bis-iron and manganese porphyrins with different substituents R on the porphyrin peripheral ring were synthesized. The cyclohexane hydroxylation catalyzed by these metalloporphyrins under mild conditions and the self-oxidation of these metalloporphyrins with PhIO were studied. The linear free energy relationship was first found for above reaction systems. Some new results and rules were obtained by carrying out correlation analysis for these two reactions. According to these results and rules, a possible mechanism for the hydrocarbon hydroxylation catalyzed by metalloporphyrins was proposed.