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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reaction Kinetics in the Ionic Liquid Methyltributylammonium Bis(Trifluoromethylsulfonyl)imide. Pulse Radiolysis Study of ·CF_3 Radical Reactions
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Reaction Kinetics in the Ionic Liquid Methyltributylammonium Bis(Trifluoromethylsulfonyl)imide. Pulse Radiolysis Study of ·CF_3 Radical Reactions

机译：离子液体甲基三丁基二甲基双（三氟甲基磺酰基）亚胺中的反应动力学。 ·CF_3自由基反应的脉冲辐解研究

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摘要

The reactions of trifluoromethyl radicals with pyrene, phenanthrene, crotonic acid, and 2-propanol (2-PrOH) in the ionic liquid methyltributylammonium bis (trifluoromethyl)imide (R_4NNTf_2) studied by pulse radiolysis. Radiolysis of R_4NNTf_2 leads to formation of solvated electrons and organic radicals, including ·CF_3. The solvated electrons do not react rapidly with the solvent and are reacted with CF_3Br to produce additional ·CF_3 radicals. The rate constants for addition of ·CF_3 radicals to pyrene and phenanthrene are determined to be (1.1 ± 0.1) * 10~7 L mol~(-1) s~(-1) and (2.6 ± 0.4) * 10~6 L mol~(-1) s~(-1), respectively. By competition kinetics, the rate constant for reaction of ·CF_3 radicals with crotonic acid is determined to be (2.7 ± 0.4) * 10~6 L mol~(-1) s~(-1), and the reaction is predominantly addition to the double bond. Competition kinetics with 2-PrOH in the absence of CF_3Br gives a rate constant of (4 ± 1) * 10~4 L mol~(-1) s~(-1) for H-abstration from 2-PrOH, but in the presence of CF_3Br, the rate constant cannot be determined because a chain reaction develops through the reduction of CF_3Br by the (CH_3)_2COH radical. The rate constants for reactions of ·CF_3 radicals in acetonitrile solutions are slightly higher, by a factor of 2.3 for pyrene and phenanthrene and a factor of 1.3 for crotonic acid. The rate constant for pyrene in aqueous acetonitrile (30% water) solutions is 4 times higher than that in the ionic liquid. Rate constants for H-abstraction and addition reactions of ·CF_3 radicals in the ionic liquid are of the same order of magnitude as in water and acetonitrile, whereas electron-transfer reactions were reported to be one or more orders of magnitude slower in ionic liquids than in water or alcohols.
机译：通过脉冲辐射分析研究了离子液体甲基三丁基双（三氟甲基）酰亚胺（R_4NNTf_2）中三氟甲基自由基与pyr，菲，巴豆酸和2-丙醇（2-PrOH）的反应。 R_4NNTf_2的辐射分解导致形成溶剂化的电子和有机基团，包括·CF_3。溶剂化的电子不会与溶剂快速反应，而是与CF_3Br反应生成额外的CF_3自由基。将·CF_3自由基加至pyr和菲的速率常数确定为（1.1±0.1）* 10〜7 L mol〜（-1）s〜（-1）和（2.6±0.4）* 10〜6 L mol〜（-1）s〜（-1）。通过竞争动力学，确定·CF_3自由基与巴豆酸反应的速率常数为（2.7±0.4）* 10〜6 L mol〜（-1）s〜（-1），反应主要是双键。在不存在CF_3Br的情况下，与2-PrOH的竞争动力学给出速率常数为（4±1）* 10〜4 L mol〜（-1）s〜（-1），用于从2-PrOH中吸氢。如果存在CF_3Br，则无法确定速率常数，因为通过（CH_3）_2COH自由基还原CF_3Br会形成链反应。 ·CF_3自由基在乙腈溶液中的反应速率常数稍高，pyr和菲的系数为2.3，巴豆酸的系数为1.3。 aqueous在乙腈水溶液（30％的水溶液）中的速率常数比离子液体中的速率常数高4倍。离子液体中·CF_3自由基的H吸收和加成反应的速率常数与在水和乙腈中的速率常数处于同一数量级，而据报道，在离子液体中电子转移反应比在离子液体中慢一个或多个数量级在水或酒精中。

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