卟啉化合物电化学性质研究 Ⅰ.5,10,15,20-四-(4-乙酰氧基苯)卟吩及其Cu、Zn、Fe、Co、Ni配合物的合成及循环伏安研究

INVESTIGATION OF ELECTROCHEMICAL CHARACTERISTICS OF PORPHYRINS I. CYCLIC VOLTAMMETRY INVESTIGATION OF 5,10, 15, 20-TETRAKIS-(4-ACETOXYPHENYL) PORPHINE AND ITS Cu, Zn, Fc, Co, Ni COMPLEXES

本文报道了5,10,15,20-四-(4-乙酰氧基苯)卟吩[T(4AOP)P]及其Cu、Zn、Fe、Co、Ni配合物的合成及其在CH_2Cl_2-0.1mol/1 TBAP体系中的循环伏安(CV)研究结果.CV实验表明:Cu^(2+)、Zn^(2+)、Ni^(2+)离子以稳定的+2价存在于T(4AOP)P中,电子转移反应在卟啉环上进行,而Fe^(3+)、Co^(2+)离子在氧化还原过程中发生价态变化。实验发现:不同金属卟啉在卟啉环上氧化还原顺序及其非均相电子转移反应速率常数与环上π电子云密度成规律性变化.

The electrochemical characteristics of 5, 10, 15, 20-tctrakis-(4-acctoxyphcnyl)-porphine and its Cu, Zn, Fe, Co, Ni complexes were investigated by Cyclic Voltammctry in CH2Cl2-0.1mol /1 TBAP. The heterogeneous electron exchange rate constants of above complexes were also calculated by the Cyclic Voltammctry technique of Nicholson. The experimental results demonstrated that Cu, Zn, Ni arc stable to electrochemical oxidation or reduction of the porphine ring, while Fe, Co undergo the changing of oxidation state. Furthermore the order of the first reduction and oxidaton half wave potential of the metal porphyrins as well as their Ks is proportional to the negative charge in the porphine ring.