物理化学学报 >> 1985, Vol. 1 >> Issue (01): 6-11.doi: 10.3866/PKU.WHXB19850102

研究论文 上一篇    下一篇

自旋捕捉技术在Ph3M(M=N, P, As, Sb, Bi)光解反应中的应用

周建威; 徐广智*; 唐有祺   

  1. 中国科学院化学所; 北京大学化学系
  • 收稿日期:1984-06-18 修回日期:1984-09-28 发布日期:1985-02-15
  • 通讯作者: 徐广智

APPLICATION OF SPIN TRAPPING TECHNIQUE TO PHOTOLYSIS OF COMPOUNDS Ph3M (M=N, P, As, Sb, Bi)

Xu Guangzhi*; Zhou Jianwei; Tang Youqi   

  1. Institute of Chemistry, Academia Sinica, Beijing; Department of Chemistry, Peking University
  • Received:1984-06-18 Revised:1984-09-28 Published:1985-02-15
  • Contact: Xu Guangzhi

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摘要：

本文用自旋捕捉技术、柱色谱与ESR波谱相结合的方法, 研究了Ph_3M(M=N, P, As, Sb, Bi)光解过程的活泼自由基。从自旋捕捉剂亚硝基特丁烷(t-BuNO)、苯亚甲基叔丁基氮氧化合物(PBN)或2,3,4,6-四甲基亚硝基苯(ND)与活泼自由基形成的自旋加合物的ESR波谱的超精细结构, 确证这些化合物光解过程中有Ph·自由基存在。从而可推断它们的光解初级过程包括Ph_3M的均裂, 即Ph_3M→Ph_2M·+Ph·。此外,因Ph—M键能的大小顺序为
Pb—P>Ph—As>Pb—Sb>Ph—Bi
所以Ph_2M·(M=As, Sb, Bi)的分解比Ph_2P·容易, 实验中只检查出Ph_2P·, 则正是所预期的。

Abstract:

Active intermediates in the photolysis processes of compounds Ph_3M (M=N, P, As, Sb, Bi) have been studied with the combination of spin trapping technique, column chromatography and ESR spectrascopy. From the hyperfine structures of the ESR spectra of the spin adducts formed between active intermediates and spin trapping reagents such as phenyl tert-butyl nitrone (PBN), nitrosobutane(t-BuNO) or nitrosodurene (ND), the free radical Ph. has been identified in the photlysis of Ph_3M (M= P, As, Sb, Bi) and Ph_2M·+Ph·. As the average bond energies of Ph—M decrease in the order Pb—P>Ph—As>Pb—Sb>Ph—BiPh_2M· (M=As, Sb, Bi) decompose much easy than that of Ph_2P·, so they could not be observed in out experiment.