中华医学超声杂志

应用化学 ›› 1996, Vol. 0 ›› Issue (6): 55-57.

• 研究简报 • 上一篇    下一篇

(TPP)Ni(Ⅱ)氧化反应的电化学和光谱电化学研究

严川伟, 王振新, 林祥钦   

  1. 中国科学院长春应用化学研究所电分析化学开放实验室, 国家电化学和光谱研究分析中心 长春 130022
  • 收稿日期:1996-02-26 修回日期:1996-06-27 出版日期:1996-12-10 发布日期:1996-12-10

Electrochemical and Spectroelectrochemical Studies on Oxidation Reactions of(TPP)Ni(Ⅱ)

Yan Chuanwei, Wang Zhenxin, Lin Xiangqin   

  1. Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chmistry of the Chinese Academy of Sciences, National Analytical Research Center of Electrochemistry and Spectroscopy, Changchun 130022
  • Received:1996-02-26 Revised:1996-06-27 Published:1996-12-10 Online:1996-12-10

PDF

370

被引次数

2

摘要： 镍卟啉是一类重要的仿生模型化合物,已有一些研究报道,然而十余年来对氧化过程的机理还认识不一.(TPP)Ni(Ⅰ)的单电子氧化通常给出较经典的环中心失电子特征,但另一些人则得到了金属中心氧化的证据,因此可能涉及到电子在络合物分子中的传递机制,值得进行深入的探讨.

关键词: 镍卟啉, 阴离子配位, 电化学, 光谱电化学

Abstract: The oxidation reactions of(TPP)Ni(Ⅱ) were reinvestigated by cyclic voltammetry and spectroelectrochemistry in the presence of F- anions in methylene chloride solution.It was found that the addition of F- led to the appearance of Ni(Ⅱ)/Ni(Ⅲ) redox step at E1/2=0.60 V(vs.SCE),which were followed by two one-electron oxidation reactions of the porphyrin ring at E1/2=0.95 V and 1.25 V,respectively.In-situ thin-layer spectra were obtained and assigned to these ring oxidized Ni(Ⅲ) species.An intermediate spectrum of (TPP)Ni(Ⅲ) was observed in a time-resolved thin-layer electrolysis.A box mechanism of F- coordination-redox reactions was proposed for this system.

Key words: nickel porphyrin, anion coordination, electrochemistry, spectroelectrochemistry

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