尾式金属卟啉配合物的研究——Ⅱ.新型尾式金属卟啉配合物的催化和载氧功能  

The Studies on Tailed Metalloporphyrin Coordination Compounds——Ⅱ.The Catalysis and Carrying Oxygen Functions of New Tailed Metalloporphyrin Coordination Compounds

作　　者：计亮年[1] 覃夏[1] 黄锦汪 

机构地区：[1]中山大学化学系/生物工程研究中心

出　　处：《中山大学学报（自然科学版）》1993年第4期1-8,共8页Acta Scientiarum Naturalium Universitatis Sunyatseni

基　　金：国家自然科学基金

摘　　要：分别研究了5-对[4-(间-吡啶氧基)丁氧基]苯基10,15,20-三苯基卟啉的Fe(Ⅱ).Fe(Ⅲ)和Co(Ⅱ)配合物的催化或载氧功能.以合成的金属卟啉、抗坏血酸和底物所组成的体系作为细胞色素P450单加氧酶的模拟体系,研究了在温和条件下对环已烷转变为环己酮、环己醇的催化作用,测定了这些体系的吸氧能力和羟化产物的产率.结果表明,尾式铁卟啉配合物Fe(Ⅲ)PyBPTPPCI 比其他简单相应铁卟啉配合物更为有效.用紫外可见光谱测定了尾式Co(Ⅱ)卟啉配合物的载氧能力,该模型化合物在室温苯溶液中呈现了可逆载氧能力,通过红外光谱进一步证明在氧合金属卟啉中的氧分子是以端基方式与中心金属Co 配位的.The catalysis or carrying oxygen functions of ferric,ferrous and cobal-tous coordination compounds of 5[p-[4-(m-pyridyloxy)butoxy]phenyl]-10,15,20-triphenylporphyrin(PyBPTPP)have been studied respectively.Hydroxylation ofeyclohexane to cyclohexanol and cyclohexanone was studied by the systems consi-sting of the synthetic metalloporphyrins,ascorbic acid and substrate as a modelsystem of cytochrome P450 monooxygenase.The dioxygen uptaking abilities ofthese systems were determined.The yields of hydroxylation products were measured by gas chromatography.The results indicated that the ferric tailed porphyrincomplex Fe(Ⅲ)PyBPTPPCI is more efficient than the simple corresponding onesfor the hydroxylation.This suggests that the presence of an axial ligand,whichis covalently linked to the porphyrin ring,greatly increase the catalytic efficien-cy.The oxygen-carrying abilities of the tailed Co(Ⅱ)porphyrin complex,Co(Ⅱ)PyBPTPP were determined by UV-Vis spectrophotometry.This model com-pound exhibited oxygen-carrying capacity reversibly in benzene solution at roomtemperature.The oxygen molecule in the end group fashion coordinate to the cen-ter cobalt of the porphyrln ring in oxymetalloporphyrin complex was proved fur-ther by infrared spectra.

关 键 词：金属卟啉 络合物 催化 载氧功能 

分 类 号：O641.4[理学—物理化学]