高等学校化学学报

高等学校化学学报 ›› 1988, Vol. 9 ›› Issue (10): 1023.

• 论文 • 上一篇    下一篇

二茂铁及其胺甲基类取代衍生物的紫外光解自由基的研究

陈德文1, 周建威1, 徐广智1, 洪仁芳2, 孙利军2, 师树简2   

  1. 1. 中国科学院化学研究所;
    2. 北京化工学院化学系
  • 收稿日期:1987-04-29 出版日期:1988-10-24 发布日期:1988-10-24
  • 通讯作者: 陈德文
  • 基金资助:

    国家自然科学基金

Studies on the Free Radicals Formed in the UV Photolysis Processes of Ferrocene and Its Amino-Methyl Substituted Derivatives

Chen Dewen1, Zhou Jianwei1, Xu Guangzhi1, Hong Renfang2, Sun Lijun2, Shi Shujian2   

  1. 1. Institute of Chemistry, AcaSemia Sinica, Beijing;
    2. Department of Chemistry, Beijing Institute of Chemical Engineering, Beijing
  • Received:1987-04-29 Online:1988-10-24 Published:1988-10-24

PDF (PC)

摘要： 本文用自旋捕捉-ESR技术研究了二茂戊铁、环二烯和胺甲基类取代二茂铁的紫外光解过程中的活泼自由基。结果表明,二茂铁光解初级过程中生成的自由基为(C5H5Fe)·和C5H5·,其衍生物光解则生成(C5H5Fe)·和RC5H4·,而(C5H5Fe)·还可以进一步分解给出C5H5和Fe。

关键词: 二茂铁, 光解, 自由基, 自旋捕捉

Abstract: Active radicals formed in the UVphotolysis of ferrocene and its amino-methyl substituted derivatives in CCl4 solution have been studied by means of spin trapp-ing-ESRtechnique. The results show that Ferrocene and substituted ferrocene are very sensitive to UVirradiation. As NDis used as trapping agent,the strong ESRsignals can be detected in photoreaction systems irradiated by UVfor only 1~3 min,but the strength of ESRsignals decay and disappear rapidly during less than 8 min and then the residual weak signal with 6 lines may be observed;when irradiation term is more than 3 min, noly 6 simple peaks may be observed.Therefore, The primary photolysis processes of ferrocene and its derivatives should produce free radicals(C5H5Fe)·, C5H5· and (C5H5Fe)·, (RC5H4)·, respectively. The active intermediate (C5H5Fe)· may be further decomposed to form C5H5· and Fe. The ESRspectrum with 25 linesmaybe is the signal of spin adducts (C5H5Fe-ND)·. The values of splitting con-stants for the spin adducts (RC5H4-ND)·, which may show ESRspectra with 6 lines, are nearly the same as for the spin adducts (C5H5-ND)·, then it can be concluded that the effect of substituent on the superfine splitting can't be observed. At the same time, three of the substituted ferrocenes can give out triplet ESRpeaks besides those 6 peaks, it means that there are two structural forms for spin adducts (RC5H4ND)·:

Key words: Ferrocene, Photolysis, Free radical, Spin trapping

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