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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Crossed Beam Reactions of the Phenyl (C_6H_5; X~2A_1) and Phenyl?d_5 Radical (C_6D_5; X~2A_1) with 1,2-Butadiene (H_2CCCHCH_3; X~1A′)
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Crossed Beam Reactions of the Phenyl (C_6H_5; X~2A_1) and Phenyl?d_5 Radical (C_6D_5; X~2A_1) with 1,2-Butadiene (H_2CCCHCH_3; X~1A′)

机译：苯基（C_6H_5; X〜2A_1）和苯基dd_5自由基（C_6D_5; X〜2A_1）与1,2-丁二烯（H_2CCCHCH_3; X〜1A'）的交叉电子束反应

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摘要

We explored the reactions on the phenyl (C_6H_5; X~2A_1) and phenyl-d5 (C_6D_5; X~2A_1) radical with 1,2-butadiene (C_4H_6; X~1A′) at a collision energy of about 52 ± 3 kJ mol~(?1) in a crossed molecular beam apparatus. The reaction of phenyl with 1,2-butadiene is initiated by adding the phenyl radical with its radical center to the π electron density at the C1/C3 carbon atom of 1,2-butadiene. Later, the initial collision complexes isomerize via phenyl group migration from the C1/C3 carbon atoms to the C2 carbon atom of the allene moiety of 1,2-butadiene. The resulting intermediate undergoes unimolecular decomposition through hydrogen atom emission from the methyl group of the 1,2-butadiene moiety via a rather loose exit transition state leading to 2-phenyl-1,3-butadiene in an overall exoergic reaction (Δ_RG = ?72 ± 10 kJ mol~(?1)). This finding reveals the strong collision-energy dependence of this system when the data are compared with those of the phenyl radical with 1,2-butadiene previously recorded at collision energies up to 160 kJ mol~(?1), with the previous study exhibiting the thermodynamically less stable 1-phenyl-3-methylallene (Δ_RG = ?33 ± 10 kJ mol~(?1)) and 1-phenyl-2-butyne (Δ_RG = ?24 ± 10 kJ mol~(?1)) to be the dominant products.
机译：我们探索了在约52±3 kJ的碰撞能量下，苯基与（1,2）丁二烯（C_4H_6; X〜1A'）与苯基（C_6H_5; X〜2A_1）和苯基-d5（C_6D_5; X〜2A_1）的反应。在交叉分子束装置中为mol·（？1）。苯基与1,2-丁二烯的反应是通过在1,2-丁二烯的C1 / C3碳原子上将其自由基中心的苯基加到π电子密度上而引发的。后来，最初的碰撞配合物通过苯基从1,2-丁二烯的丙二烯部分的C1 / C3碳原子迁移到C2碳原子而异构化。所得的中间体通过氢原子从1,2-丁二烯部分的甲基发射，并通过相当宽松的出口过渡态进行单分子分解，从而在整个放热反应中导致生成2-苯基-1,3-丁二烯（Δ_RG=？72 ±10 kJ mol〜（？1））。这一发现揭示了当将该数据与先前在高达160 kJ mol〜（？1）的碰撞能量下记录的带有1,2-丁二烯的苯基进行比较时，该系统具有很强的碰撞能量依赖性，而先前的研究表明热力学上不稳定的1-苯基-3-甲基丙烯（Δ_RG=Δ33±10 kJ mol〜（Δ1））和1-苯基-2-丁炔（Δ_RG=Δ24±10 kJ mol〜（Δ1））至成为主导产品。

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