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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Substituent effects on the nonradical reactivity of 4-dehydropyridinium cation
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Substituent effects on the nonradical reactivity of 4-dehydropyridinium cation

机译：取代基对4-脱氢吡啶鎓阳离子非自由基反应性的影响

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摘要

Recent studies have shown that the reactivity of the 4-dehydropyridinium cation significantly differs from the reactivities of its isomers toward tetrahydrofuran. While only hydrogen atom abstraction was observed for the 2- and 3-dehydropyridinium cations, nonradical reactions were observed for the 4-isomer. In order to learn more about these reactions, the gas-phase reactivities of the 4-dehydropyridinium cation and several of its derivatives toward tetrahydrofuran were investigated in a Fourier transform ion electron resonance mass spectrometer. Both radical and nonradical reactions were observed for most of these positively charged radicals. The major parameter determining whether nonradical reactions occur was found to be the electron affinity of the radicals-only those with relatively high electron affinities underwent nonradical reactions. The reactivities of the monoradicals are also affected by hydrogen bonding and steric effects.
机译：最近的研究表明，4-脱氢吡啶鎓阳离子的反应性明显不同于其异构体对四氢呋喃的反应性。虽然对于2-和3-脱氢吡啶鎓阳离子仅观察到氢原子提取，但对于4-异构体观察到非自由基反应。为了更多地了解这些反应，在傅立叶变换离子电子共振质谱仪中研究了4-脱氢吡啶鎓阳离子及其衍生物对四氢呋喃的气相反应性。对于大多数这些带正电荷的自由基，都观察到自由基反应和非自由基反应。发现确定非自由基反应是否发生的主要参数是自由基的电子亲和力，只有具有较高电子亲和力的那些自由基才进行非自由基反应。自由基的反应性也受到氢键和空间效应的影响。

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