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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Condensation Reactions between 1,3-Butadiene Radical Cation and Acetylene in the Gas Phase
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Condensation Reactions between 1,3-Butadiene Radical Cation and Acetylene in the Gas Phase

机译：1,3-丁二烯自由基阳离子与乙炔在气相中的缩合反应

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摘要

The present paper reports the first experimental and theoretical results concerning the reaction of [1,3-butadiene]~(+·) radical cation, 1, with neutral acetylene C_2H_2, 2 Experiments conducted in the gas phase and under low pressure in an FT-ICR mass spectrometer show that the reaction leads to C_6H_7~+ ions. Complete analysis of the experimental data reveals that a mixture of three distinct C_6H_7~+ species is produced: it consists of benzenium ions, a (≈55%), and the two most stable protonated forms of fulvene (i.e., a-protonated fulvene, b, ≈25%, and bicyclo[3,1,0]-hexenyl, c, ≈20%). A mechanism, supported by ab initio molecular orbital calculations at the UMP2/6-311+G(d,p)//UMP2/6-31G(d) + ZPE level, is proposed to account for the observations. A Diels-Alder type reaction involving stepwise bond formation is at the origin of ionized 1,4-cyclohexadiene, 5, the first precursor of the benzenium ion a. Starting from 5, hydrogen-atom migrations and ring-contraction processes generate the precursors of the two other products, b and c.
机译：本文报道了有关[1,3-丁二烯]〜（+·）自由基阳离子[1]与中性乙炔C_2H_2 [2]的反应的第一个实验和理论结果。 -ICR质谱仪显示该反应导致C_6H_7〜+离子。对实验数据的完全分析显示，生成了三种不同的C_6H_7〜+物种的混合物：它由苯离子（约55％）和两种最稳定的质子形式的富烯（即，质子化的富烯， b，≈25％，双环[3,1,0]-己烯基，c，≈20％）。提出了一种机制，该机制由UMP2 / 6-311 + G（d，p）// UMP2 / 6-31G（d）+ ZPE级别的从头算分子轨道计算来支持，以解释这些现象。涉及逐步形成键的Diels-Alder型反应是在离子化的1,4-环己二烯5（苯系离子a的第一个前体）的起点。从5开始，氢原子迁移和环收缩过程会生成其他两种产物b和c的前体。

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