Decay reactions of aryldiazenyl radicals in solution.
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概要
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The decay processes of aryldiazenyl radicals were studied by using a time-resolved ESR method. The first order rate constants of decomposition were determined at −117–−48 °C in cyclopropane solutions in the presence or absence of olefins. Aryldiazenyl radicals were relatively persistent and the <I>k</I><SUB>1</SUB> of phenyldiazenyl-<I>d</I><SUB>5</SUB> at −96 °C in cyclopropane was 34 s<SUP>−1</SUP>. The <I>k</I><SUB>1</SUB> of 20 aryldiazenyl radicals at −96 °C afforded a ρ value of +1.53 (<I>r</I>=0.91) in a Hammett plot. Activation energies ranged from 46.2 to 25.2 kJ mol<SUP>−1</SUP> and the frequency factors, log A, from 13.2 to 8.2 s<SUP>−1</SUP>. The second-order decay rates were measured at the initial period of the decay process at lower temperatures, in a batch system (cyclopropane) and in a flow system (isohexane). The rate constant of phenyldiazenyl-<I>d</I><SUB>5</SUB> in cyclopropane was 9.2·10<SUP>−5</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP> at −93 °C and the Arrhenius parameters were <I>E</I><SUB>a</SUB>=23.5 kJ mol<SUP>−1</SUP> and log<I>A</I>=12.77 M<SUP>−1</SUP> s<SUP>−1</SUP>, respectively.
- 公益社団法人 日本化学会の論文
著者
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Date Munehiro
The Institute Of Physical And Chemical Research
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Koike Akemi
Department Of Biomolecular Science Faculty Of Science Toho University
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Mori Atsushi
Department Of Applied Physics Faculty Of Engineering University Of Fukui
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Suehiro Tadashi
Department of Chemistry Faculty of Science The University of Tokyo
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Masuda Seiichi
Department of Chemistry, Faculty of Science, Gakushuin University
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Nakausa Ryuichi
Department of Chemistry, Faculty of Science, Gakushuin University
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Taguchi Masamichi
Department of Chemistry, Faculty of Science, Gakushuin University
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Koike Akemi
Department of Chemistry, Faculty of Science, Gakushuin University
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