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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reactivity of the Gaseous Radical Cations of Trimethylenemethane and 2-Isopropylidenecyclopentane-1,3-diyl
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Reactivity of the Gaseous Radical Cations of Trimethylenemethane and 2-Isopropylidenecyclopentane-1,3-diyl

机译：三亚甲基甲烷和2-异亚丙基环戊烷-1,3-二基的气体自由基阳离子的反应性

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摘要

The radical cation of trimethylenemethane (TMM~(·+)) and a derivative, 2-isopropylidenecyclopentane-1,3-diyl, were generated by electron ionization of methylenecyclopropane (MCP) and electron-ionization-induced loss of nitrogen from 7-isopropylidene-2,3-diazabicyclo[2.2.1]hept-2-ene, respectively, in a Fourier transform ion cyclotron resonance mass spectrometer. The two radical cations were isolated and their products and reaction rates with various gaseous reagents were measured. TMM~(·+) displays radical-type reactivity, e.g., it slowly abstracts a hydrogen atom from benzeneselenol and a thio- or selenomethyl radical from dimethyl disulfide and dimethyl diselenide, respectively. This reactivity distinguishes it from the isomeric 1,2- and 1,3-butadiene radical cations. Surprisingly, however, the TMM~(·+) undergoes electron transfer reactions in addition to radical reactions. The difference between the adiabatic recombination energy of TMM~(·+) (9.2 ± 0.1 eV) and the adiabatic ionization energy of MCP (9.4 ± 0.1 eV; the earlier literature estimate is ≤9.57 eV), which were experimentally determined in this work, indicates that the above electron abstraction reactions likely involve cyclization to yield MCP (and not TMM) as the final neutral product. In sharp contrast to TMM~(·+), the sterically hindered 2-isopropylidenecyclopentane-1,3-diyl radical cation is unreactive toward most of the reagents studied, including benzeneselenol, dimethyl disulfide, and dimethyl diselenide. The recombination energy of this TMM-type radical cation (and thus, the ionization energy of the 2-isopropylidenecyclopentane-1,3-diyl biradical) was measured to be 7.8 ± 0.1 eV.
机译：三亚甲基甲烷（TMM〜（·+））及其衍生物2-异亚丙基环戊烷-1,3-二基的自由基阳离子是通过亚甲基环丙烷（MCP）的电子电离和电子电离引起的氮从7-异亚丙基的损失而产生的-2，3-二氮杂双环[2.2.1]庚-2-烯分别在傅里叶变换离子回旋共振质谱仪中。分离了两个自由基阳离子，并测量了它们的产物和与各种气态试剂的反应速率。 TMM_（·+）显示出自由基型反应性，例如，它缓慢地从苯硒酚中提取氢原子，并从二甲基二硫化物和二甲基二硒化物中分别提取出硫代或硒代甲基。该反应性使其与异构的1,2-和1,3-丁二烯自由基阳离子区分开。然而，令人惊讶的是，除了自由基反应之外，TMM_（·+）还经历了电子转移反应。 TMM〜（·+）的绝热复合能（9.2±0.1 eV）与MCP的绝热电离能（9.4±0.1 eV;较早的文献估计是≤9.57eV）之差，这是通过实验确定的表示上述电子抽象反应可能涉及环化反应，以产生MCP（而非TMM）作为最终的中性产物。与TMM〜（+）形成鲜明对比的是，空间受阻的2-异亚丙基环戊烷-1,3-二基自由基阳离子与大多数研究的试剂（包括苯硒酚，二甲基二硫化物和二甲基二硒化物）没有反应。该TMM型自由基阳离子的重组能（因此，2-异亚丙基环戊烷-1，3-二基双自由基的电离能）为7.8±0.1eV。

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