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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Combined Crossed Molecular Beam and ab Initio Investigation of the Multichannel Reaction of Boron Monoxide (BO; X~2Σ~+) with Propylene (CH_3CHCH_2; X1A'): Competing Atomic Hydrogen and Methyl Loss Pathways
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Combined Crossed Molecular Beam and ab Initio Investigation of the Multichannel Reaction of Boron Monoxide (BO; X~2Σ~+) with Propylene (CH_3CHCH_2; X1A'): Competing Atomic Hydrogen and Methyl Loss Pathways

机译：交叉分子束与从头算相研究一氧化硼（BO; X〜2Σ〜+）与丙烯（CH_3CHCH_2; X1A'）的多通道反应：竞争性氢原子和甲基损失途径

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The reaction dynamics of boron monoxide (~(11)BO; X~2Σ~+) with propylene (CH_3CHCH_2; X~1A') were investigated under single collision conditions at a collision energy of 22.5 ± 1.3 kJ mol~(-1). The crossed molecular beam investigation combined with ab initio electronic structure and statistical (RRKM) calculations reveals that the reaction follows indirect scattering dynamics and proceeds via the barrierless addition of boron monoxide radical with its radical center located at the boron atom. This addition takes place to either the terminal carbon atom (C1) and/or the central carbon atom (C2) of propylene reactant forming ~(11)BOC_3H_6 intermediate(s). The long-lived ~(11)BOC_3H_6 doublet intermediate(s) underwent unimolecular decomposition involving at least three competing reaction mechanisms via an atomic hydrogen loss from the vinyl group, an atomic hydrogen loss from the methyl group, and a methyl group elimination to form cis-/trans-1-propenyl-oxo-borane (CH_3CHCH~(11)BO), 3-propenyl-oxo-borane (CH_2CHCH_2~(11)BO), and ethenyl-oxo-borane (CH_2CH~(11)BO), respectively. Utilizing partially deuterated propylene (CD_3CHCH_2 and CH_3CDCD_2), we reveal that the loss of a vinyl hydrogen atom is the dominant hydrogen elimination pathway (85 ± 10%) forming cis-/trans-1-propenyl-oxo-borane, compared to the loss of a methyl hydrogen atom (15 ± 10%) leading to 3-propenyl-oxo-borane. The branching ratios for an atomic hydrogen loss from the vinyl group, an atomic hydrogen loss from the methyl group, and a methyl group loss are experimentally derived to be 26 ± 8%:5 ± 3%:69 ± 15%, respectively; these data correlate nicely with the branching ratios calculated via RRKM theory of 19%:5%:75%, respectively.
机译：在单一碰撞条件下以22.5±1.3 kJ mol〜（-1）的碰撞能量研究了一氧化硼（〜（11）BO; X〜2Σ〜+）与丙烯（CH_3CHCH_2; X〜1A'）的反应动力学。交叉分子束研究与从头算电子结构和统计（RRKM）计算相结合，揭示了该反应遵循间接散射动力学，并且通过其自由基中心位于硼原子的一氧化硼自由基的无阻添加而进行。该加成发生在形成〜（11）BOC_3H_6中间体的丙烯反应物的末端碳原子（C1）和/或中心碳原子（C2）上。长寿命的〜（11）BOC_3H_6双峰中间体经历了至少三个竞争反应机理的单分子分解，该反应机理是乙烯基发生原子氢损失，甲基发生原子氢损失以及甲基消除形成顺式/反式-1-丙烯基-氧硼烷（CH_3CHCH〜（11）BO），3-丙烯基-氧代硼烷（CH_2CHCH_2〜（11）BO）和乙烯基-氧代硼烷（CH_2CH〜（11）BO ）， 分别。利用部分氘代的丙烯（CD_3CHCH_2和CH_3CDCD_2），我们发现，与损失相比，乙烯基氢原子的损失是形成顺式/反式-1-丙烯基-氧代硼烷的主要氢消除途径（85±10％）甲基氢原子（15±10％）产生3-丙烯基-氧-硼烷。乙烯基的原子氢损失，甲基的原子氢损失和甲基基团的支化比率分别实验得出为26±8％：5±3％：69±15％。这些数据分别与通过RRKM理论计算的19％：5％：75％的支化率很好地相关。

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