金属卟啉催化性能与金属原子电子构型关系  

Study on Relationships Between Biocatalytic Properties of Metalloporphyrins and Electronic Configuration of Metal Atoms

作　　者：郭灿城[1] 李枝蓬[1] 梁本熹[1] 张晓兵[1] 

机构地区：[1]湖南大学化学化工系

出　　处：《湖南大学学报（自然科学版）》1996年第5期66-70,共5页Journal of Hunan University:Natural Sciences

基　　金：国家自然科学基金

摘　　要：合成了三种具有不同电子排布的金属卟啉，ＴＰＰＦｅ（Ⅲ）Ｃｌ，ＴＰＰＣｏ（Ⅱ）和［ＴＰＰＦｅ（Ⅲ）］２Ｏ，并用它们模拟细胞色素Ｐ－４５０单充氧酶在温和条件下催化环己烷的氧化反应．结果表明，金属卟啉的仿生催化性能与它们的磁场性质有关．对ＰｈＩＯ氧化环己烷的反应，具有低自旋排布的ＴＰＰＣｏ（Ⅱ）和由于反铁磁耦合而呈现抗磁性的［ＴＰＰＦｅ（Ⅲ）］２Ｏ没有催化性能，而高自旋排布的ＴＰＰＦｅ（Ⅲ）Ｃｌ具有催化性能．实验还表明，如果将金属卟啉与合适的有机配体配位而使金属原子的电子排布方式发生改变而导致磁场性质改变以后，金属卟啉的仿生催化性能也随之发生改变。metalloporphyrins with different electronic arrangements,TPPFe(Ⅲ)Cl,TPPCo(Ⅱ)and [TPPFe(Ⅲ)]2O are synthesized.The cyclohexane hydroxylation with PhIO catalyzed by these porphyrins at moderate conditions is carried out. The imitated catalytic properties of the metalloporphyrins are found to be realated to the magnetic properties caused by the the electron spin state of metal atoms.TPPCo(Ⅱ)with S =1/2 low spin arrangement and [TPPFe(Ⅲ)]2O with antiferromagnetic coupling do not catalyze cyclohexane hydroxylation with PhIO,but the ferromagnetic TPPFe(Ⅲ) Cl with high spin arrangement does.The researches show also that imitated catalytic properties of metalloporphyrins change with the change of the electron spin arrangement of metal atoms caused by coordiation between metalloporphyrins and organic ligands.

关 键 词：金属卟啉 催化 羟基化反应 电子结构 金属原子 

分 类 号：O627.7[理学—有机化学]