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化学学报
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化学学报 ›› 1993, Vol. 51 ›› Issue (11): 1099-1105. 上一篇    下一篇

研究论文

氯离子存在下四苯基卟啉合锰的电化学和现场光谱电化学II. 氧化过程

李志丽;林祥钦   

  1. 中国科学院长春应用化学研究所;中国科学院电分析化学开放研究实验室
  • 发布日期:1993-11-15

Electrochemical and In-Situ spectroelectrochemical study of (tetraphenylporphinato) manganese(III) perchlorate in the presence of chloride anions. II. oxidation processes

LI ZHILI;LIN XIANGQIN   

  • Published:1993-11-15

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本文研究了氯离子滴定过程中四苯基卟啉合锰氧化过程的常规循环伏安、薄层循环伏安及现场紫外-可见光谱电化学行为。发现在1摩尔比的Cl^-存在下, 四苯基卟啉合锰经历了Mn(III)/Mn(III)环阳离子自由基及进一步氧化为环两价阳离子的过程, 并伴随有异卟啉生成的后行化学反应, 当2摩尔比的Cl^-存在时, 反应机理转变为Mn(III)/Mn(IV), Mn(IV)/Mn(IV)环阳离子自由基并伴随有异卟啉生成反应的两个氧化步骤。提出了与这一滴定过程相关的氧化还原反应机理。

关键词: 紫外分光光度法, 氧化, 反应机理, 氯离子, 锰络合物, 循环伏安法, 光谱电化学, 四苯基卟啉

An investigation of electrode oxidation processes of (tetraphenylporphinato)manganese(III) perchlorate, (TPP)Mn(III)ClO4, was carried out during the titration of chloride anions by conventional cyclic voltammetry, thin-layer cyclic voltammetry and spectroelectrochem. It was demonstrated that in the presence of one equivalent amount of Cl1-, the first one electron oxidation reaction corresponds to the Mn(III)/cation radical oxidation, and the 2nd one electron oxidation corresponds to the cation radical/dication generation followed by an isoporphyrin formation reaction, however in the presence of 2 equiv amount of Cl1-, the first one electron oxidation of Mn(III) gives Mn(IV) porphyrin and the 2nd one electron oxidation generates cation radicals of Mn(IV) followed by an isoporphyrin formation reactions. Mechanisms of these redox processes are postulated.

Key words: ULTRAVIOLET SPECTROPHOTOMETRY, OXIDATION, REACTION MECHANISM, CHLORINE ION, MANGANESE COMPLEX, CYCLOVOLTAMGRAPH

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