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合成和表征了一系列以柔韧烷氧链相连的 o/o型单核铁卟啉二聚体 .利用 X-光电子能谱 ( XPS)研究了卟啉二聚体中由自由卟啉环向铁卟啉环发生的分子内电子转移 .考察了在以分子氧为氧源还原剂存在的温和条件下 ,该类配合物模拟细胞色素 P450酶对环己烷羟化反应的催化性能 .结果表明 ,该系列 o/o型单核铁卟啉二聚体的催化性能明显优于相应的铁卟啉单体 Fe TPPCl.随着烷氧链的增长 ,催化活性次序为 :C2 >C4 >C6>C8>C10 .该次序与单核铁卟啉二聚体的特定构象引起的立体位阻和分子内电子转移密切相关 .
A series of o / o mononuclear iron porphyrin dimers linked by flexible alkoxides were synthesized and characterized.X-ray photoelectron spectroscopy (XPS) was used to study the transition from porphyrin dimers to The intramolecular electron transfer of the porphyrin ring was investigated.It was investigated that under the mild conditions of molecular oxygen as oxygen source reductant, this kind of complex mimics the catalytic activity of cytochrome P450 on the hydroxylation of cyclohexane.The results showed that, The catalytic activity of the o / o mononuclear iron porphyrin dimer was obviously better than that of the corresponding iron porphyrin monomer Fe TPPCl. With the increase of alkoxide chain, the order of catalytic activity was C2> C4> C6> C8 > C 10. This order is closely related to steric hindrance and intramolecular electron transfer due to the specific conformation of mononuclear iron porphyrin dimer.