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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; (XII)-I-2) with Methylacetylene (CH3CCH; X(1)A(1)) and D4-Methylacetylene (CD3CCD; X(1)A(1))
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A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; (XII)-I-2) with Methylacetylene (CH3CCH; X(1)A(1)) and D4-Methylacetylene (CD3CCD; X(1)A(1))

机译：通过硅氢基自由基（SiH;（XII）-I-2）与甲基乙炔（CH3CCH; X（ 1）A（1））和D4-甲基乙炔（CD3CCD; X（1）A（1））

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The bimolecular gas-phase reactions of the ground-state silylidyne radical (SiH; (XII)-I-2) with methylacetylene (CH3CCH; X(1)A(1)) and D4-methylacetylene (CD3CCD; X(1)A(1)) were explored at collision energies of 30 kJ mo1(-1) under single-collision conditions exploiting the crossed molecular beam technique and complemented by electronic structure calculations. These studies reveal that the reactions follow indirect scattering dynamics, have no entrance barriers, and are initiated by the addition of the silylidyne radical to the carbon-carbon triple bond of the methylacetylene molecule either to one carbon atom (C1; [i1]/[i2]) or to both carbon atoms concurrently (C1-C2; [i3]). The collision complexes [i1]/[i2] eventually isomerize via ring-closure to the c-SiC3H5 doublet radical intermediate [i3], which is identified as the decomposing reaction intermediate. The hydrogen atom is emitted almost perpendicularly to the rotational plane of the fragmenting complex resulting in a sideways scattering dynamics with the reaction being overall exoergic by -12 +/- 11 kJ mol(-1) (experimental) and -1 +/- 3 kJ mol(-1) (computational) to form the cyclic 2-methyl-1-silacycloprop-2-enylidene molecule (c-SiC3H4; p1). In line with computational data, experiments of silylidyne with D4-methylacetylene (CD3CCD; X(1)A(1)) depict that the hydrogen is emitted solely from the silylidyne moiety but not from methylacetylene. The dynamics are compared to those of the related D1-silylidyne (SiD; (XII)-I-2) acetylene (HCCH; X-1 Sigma(+)(g)) reaction studied previously in our group, and from there, we discovered that the methyl group acts primarily as a spectator in the title reaction. The formation of 2-methyl-1-silacycloprop-2-enylidene under single collision conditions via a bimolecular gas-phase reaction augments our knowledge of the hitherto poorly understood silylidyne (SiH; (XII)-I-2) radical reactions with small hydrocarbon molecules leading to the synthesis of organosilicon molecules in cold molecular clouds and in carbon-rich circumstellar envelopes.
机译：基态甲硅烷基（SiH;（XII）-I-2）与甲基乙炔（CH3CCH; X（1）A（1））和D4-甲基乙炔（CD3CCD; X（1）A）的双分子气相反应（1））是利用交叉分子束技术并通过电子结构计算在单碰撞条件下以30 kJ mo1（-1）的碰撞能量进行探索的。这些研究表明，这些反应遵循间接散射动力学，没有进入障碍，并且是通过在甲基乙炔分子的碳-碳三键上向一个碳原子上加甲硅烷基（C1; [i1] / [ [i2]）或两个碳原子同时存在（C1-C2; [i3]）。碰撞配合物[i1] / [i2]最终通过闭环异构化为c-SiC3H5双峰自由基中间体[i3]，该中间体被确定为分解反应中间体。氢原子几乎垂直于片段化复合物的旋转平面发射，从而产生侧向散射动力学，反应的整体放热为-12 +/- 11 kJ mol（-1）（实验性）和-1 +/- 3 kJ mol（-1）（计算值）形成环状2-甲基-1-硅环丙-2-烯基分子（c-SiC3H4; p1）。与计算数据相符，甲硅烷基炔与D4-甲基乙炔（CD3CCD; X（1）A（1））的实验表明，氢仅从甲硅烷基炔部分而不是甲基乙炔释放。将动力学与先前在我们小组中研究的相关D1-甲硅烷基（SiD;（XII）-I-2）乙炔（HCCH; X-1 Sigma（+）（g））反应的动力学进行比较，发现甲基主要在标题反应中充当旁观者。在单碰撞条件下通过双分子气相反应形成的2-甲基-1-silacycloprop-2-enylidenene扩大了我们对迄今了解甚少的与小烃的甲硅烷基（SiH;（XII）-I-2）自由基反应的了解分子导致冷分子云和富碳的恒星包膜中有机硅分子的合成。

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