物理化学学报 >> 2000, Vol. 16 >> Issue (02): 111-115.doi: 10.3866/PKU.WHXB20000204

研究论文 上一篇    下一篇

吲哚酚衍生物的结构--式电位关系及电氧化机理

朱永春, 程广金, 董绍俊   

  1. 中国科学院长春应用化学研究所电分析化学开放研究室，长春 130022
  • 收稿日期:1999-03-09 修回日期:1999-06-25 发布日期:2000-02-15
  • 通讯作者: 董绍俊

The Relation Between Formal Potential and Structure of Indophenols and Molecular Mechnism of Electrooxidation

Zhu Yong-Chun, Cheng Guang-Jin, Dong Shao-Jun   

  1. Laboratory of Electroanalytical Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022
  • Received:1999-03-09 Revised:1999-06-25 Published:2000-02-15
  • Contact: Dong Shao-Jun

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摘要：

以半经验分子轨道方法计算吲哚酚衍生物的分子结构参数. 以主因子分析法和多元线性回归法研究了吲哚酚衍生物的式电位与其分子结构参数间的关系.研究发现, 在所选择的19个分子结构参数中, 双中心电子交换能(Eex(2)/eV), O -C键的共振能(Er(C1-O)/eV)和分子的电离势(Ip/eV)与其式电位有较好的相关性. 其回归方程为:y=1.47×10-3Eex(2) -5.74×10-2 Er(C1-O) -1.41×10-2Ip(RC=0.9999,SD=0.00424). 由分子结构与式电位关系及中间产物的稳定性可推测, 在吲哚酚的氧化机理中氢的电离反应优先于电子转移过程.

关键词: 吲哚酚衍生物, 式电位, 分子结构参数, 主因子-回归法, 氧化还原反应分子机理

Abstract:

The molecular structural parameters of indophenol and its derivatives were calculated by semi empirical molecular orbital quantum chemical method. The relation between molecular structural parameters and formal potentials was analyzed by principal factor analysis and multiple linear regression method. It was found that the formal potential of indophenols has a good relation with two cent er electron exchange energy, Eex(2), resonance energy of O-C bond, Eex(C1-O),and molecular ionization potential, Ip, among 19 molecular structural parameters. The regression equation is E0′= 1.47×10－3 Eex(two)－5.74×10－2 Eex(C1－O)－1.41 ×10－2 Ip with RC=0.9999 and SD=0.00424.It was confirmed by the relation between structure parameters and formal potentials, and the thermodynamic stability of its intermediate products that the H＋ionization is prior to the electron transfer step in the oxidation mechanism.

Key words: Indophenols, Formal potential, Molecular structural parameters, Principal factor analysis and regression, Molecular mechanism of redox reaction