Direct and indirect hydrogen abstraction in Cl + alkene reactions.
Direct and indirect hydrogen abstraction in Cl + alkene reactions.
复制标题
Cl 烯烃反应中的直接和间接夺氢。
DOI：
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发表时间：
2014
影响因子：
2.9
通讯作者：
S. Vázquez
中科院分区：
文献类型：
--
作者：
T. J. Preston;G. T. Dunning;A. Orr;S. Vázquez
氯原子和丙烯之间的反应可以通过直接抽氢或通过氯丙基加成络合物导致HCl形成。除非发生稳定碰撞，氯丙基自由基将分解成反应物或形成HCl和烯丙基产物。使用速度图成像来测量HCl产物的量子态和速度提供了对反应动力学的观察，其显示了直接和间接反应机制的迹象。反应的模拟轨迹突出了直接H-提取途径的作用，并且所得的模拟散射图像显示出与测量的合理的一致性。模拟还显示了氯丙基络合物内远离平衡几何形状的Cl原子的大偏移的重要性，并且这些大振幅运动是HCl +烯丙基碎裂的最终驱动力。气相测量较大的烯烃，2-甲基丙烯和2，3-二甲基丁-2-烯，显示略有不同的产品分布，但仍然具有相似的反应动力学。目前的一套实验为液相双分子反应提供了现成的扩展。
Reactions between Cl atoms and propene can lead to HCl formation either by direct H abstraction or through a chloropropyl addition complex. Barring stabilizing collisions, the chloropropyl radical will either decompose to reactants or form HCl and allyl products. Using velocity-map imaging to measure the quantum state and velocity of the HCl products provides a view into the reaction dynamics, which show signs of both direct and indirect reaction mechanisms. Simulated trajectories of the reaction highlight the role of the direct H-abstraction pathways, and the resultant simulated scattering images show reasonable agreement with measurement. The simulations also show the importance of large excursions of the Cl atom far from equilibrium geometries within the chloropropyl complex, and these large-amplitude motions are the ultimate drivers toward HCl + allyl fragmentation. Gas-phase measurements of larger alkenes, 2-methylpropene and 2,3-dimethylbut-2-ene, show slightly different product distributions but still feature similar reaction dynamics. The current suite of experiments offers ready extensions to liquid-phase bimolecular reactions.
氯化溶剂中 Cl 原子与 2,3-二甲基丁-2-烯反应的振动解析动力学
DOI：
10.1039/c2sc21267f
发表时间：
2013
期刊：
Chem. Sci.
影响因子：
--
作者：
Abou-Chahine F
通讯作者：
Abou-Chahine F