Synthetic and Electrochemical Studies of Porphyrin Derivatives and Developement of Artificial Metalloenzymes

制备了Meso-二苯基卟啉II(DPEP)，并用循环伏安法研究了其氧化还原行为，并与Meso-四苯基卟啉(TPP)、八乙基卟啉(OEP)和原卟啉IX二甲酯(PPIXDME)进行了比较。DPEP的氧化还原电位和碱度数据与OEP和PPIXDME相似。通过赤道和轴向配位效应研究了高自旋中二芳基二芳基叶基卟啉II(DAEP)铁(III)络合物的氧化还原行为。高自旋铁卟啉的氧化还原电位只受赤道配位体的影响，而轴向配位体对高自旋铁卟啉的金属氧化还原反应有显著的影响，无论是由卟啉环还是金属生成的氧化还原电位都可以通过考察取代基的依赖关系来学习。杂阴离子配位的Fe(III)卟啉出现了一个新的阳极峰，而相应的Fe(III)氯化物则没有观察到。用控制电位电解法氧化高自旋Fe(III)卟啉得到单电子氧化产物，并用分光光度法(UV，V，IR)和电子自旋共振(ESR)对其进行了表征。苯酚连接的Fe(III)卟啉的单电子氧化产物不是Fe(IV)卟啉的Fe(III)-阳离子自由基，而是一个高自旋的Fe(III)卟啉在轴向位置连接了一个单电子氧化的酚氧化物。

meso-Diphenyletioporphyrin II (DPEP) was prepared and its redox behaviors were studied by cyclic voltammetryin comparison with meso- tetraphenylporphine (TPP), octaethylporphyrin (OEP), and protoporphyrin IX dimethylester (PPIXDME). the redox potentials and basicity data of DPEP were found to be similar to those of OEP and PPIXDME.Redox behavior of high-spin meso-diaryletioporphyrin II (DAEP) iron(III) complexes were investigated through both of equatorial and axial ligand effects. The redox potentials due to porphyrin ring were affected only by the equatorial ligands, whereas the axial ligands affected remarkably the metal redox reactions of high-spin ferric porphyrins, whether the redox potentials due to porphyrin ring or metal could be learned by examining the dependence of the redox potentials on substituents.Redox behaviors of high-spin phenoxy and phenylthio Fe(III) porphyrins were investigated by cyclic voltammetry. The hetero-anion-ligated Fe(III) porphyrins showed a new anodic peak not observed for corresponding Fe(III) porphyrin chloride. High-spin Fe(III) porhpyrins were oxidized by controlled potential electrolysis to give the single-electron oxidation products, which were characterized by spectrophotometric (UV,V,IR) and electron spin rsonance (ESR) measurements. The single-electron oxidation products of phenoxide-ligated Fe(III) porphyrins were not Fe(III) prphyrin -cation radical of Fe(IV) prphyrin but a high-spin Fe(III) porphyrin ligated a single-electron oxidized phenoxide at an axial position.