Laser-flash photolysis study of dithiobis (tetrazole); Reactivities of tetrazole-thio radical

Maksudul M. Alam, Akira Watanabe, Osamu Ito

研究成果: Article査読

7 被引用数 (Scopus)

抄録

The photo-cleavage of S - S bond of 5,5′-dithiobis (1-phenyl-1H-tetrazole) has been studied by the nanosecond-laser flash photolysis method. The transient absorption band at ca. 430 nm was attributed to 1-phenyl-1H-tetrazole-5-thio radical forming by the S - S bond fission. For the reaction with conjugated dienes, an addition reaction takes place forming the S - C bond, suggesting that unpaired electron of the radical localizes mainly on the S-atom. From the decay rates of the radical, the addition reaction rate constant for 2-methyl-1,3-butadiene is evaluated to be 5.5 × 109 M-1 s-1 in THF at 23°C, which is as fast as diffusion controlled limit. The reactivity of the radical is ca. 100 times higher than that of the PhS. The reactivity of the thio radical to O2 was too low to evaluate, which is one of the characteristics of a S-centered radical. The rate constant for 1,4-cyclohexadienene (1.4 × 108 M-1 s-1) is larger than that of cyclohexene (2.8 × 107 M-1 s-1), suggesting the hydrogen abstraction is a main reaction. The MO calculations have been performed for these radicals to reveal the reason of the high reactivity of the radical.

本文言語English
ページ(範囲)405-411
ページ数7
ジャーナルInternational Journal of Chemical Kinetics
28
6
DOI
出版ステータスPublished - 1996

ASJC Scopus subject areas

  • 生化学
  • 物理化学および理論化学
  • 有機化学
  • 無機化学

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