【摘要】 采用循环伏安法对一系列四苯基金属卟啉的电化学氧化还原性质进行了研究,考察了四苯基金属卟啉的第一还原电位与其催化氧化α蒎烯性能的关系.结果表明,各四苯基金属卟啉催化空气氧化α蒎烯转化率的大小顺序为TPPMnⅢCl >TPPCoⅢCl>TPPFeⅢCl>TPPCuⅡ≈TPPNiⅡ≈TPPZnⅡ,除TPPCoⅢCl外,基本与其第一还原电位的大小顺序一致.随着卟啉环上取代基供电子能力的减弱,各取代基铁卟啉和锰卟啉的第一还原电位E1值均逐渐减小,表现在催化体系中是它们越容易被还原而引发反应,催化氧化α蒎烯的转化率逐渐升高.四苯基铁卟啉和锰卟啉的第一还原电位E1与其卟啉环上对位取代基常数σ之间均有良好的线性关系更多还原

【Abstract】 The electrochemical property of some metalloporphyrins and its relationship to the catalytic oxidation of α-pinene were investigated by cyclic voltammetry method. The results showed that the conversion of α-pinene oxidation catalyzed by the metalloporphyrins with air decreased in the order TPPMn~ⅢCl>TPPCo~ⅢCl>TPPFe~ⅢCl>TPPCu~Ⅱ≈TPPNi~Ⅱ≈TPPZn~Ⅱ,which was in accordance with the order of their first reduction potentials except TPPCo~ⅢCl. With the decrease of the electron-releasing capability of different substituents in the porphyrin rings, the first reduction potentials of the substitutional iron tetraphenylporphyrins and manganese tetraphenylporphyrins reduced, and the conversion of α-pinene oxidation catalyzed by the metalloporphyrins increased, which indicated that the metalloporphyrins were easily reduced to initiate the catalytic reaction. A good linear relationship was obtained between the first reduction potentials and the characteristic constants ( σ ~*) of meso -position substituents on the porphyrin ring of the iron tetraphenylporphyrins and manganese tetraphenylporphyrins.更多还原