Directed Gas Phase Formation of Silene (H 2 SiCH 2 )
Directed Gas Phase Formation of Silene (H 2 SiCH 2 )
复制标题
硅烷(H 2 SiCH 2 )的定向气相形成
DOI：
10.1002/chem.202002359
复制
发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Kaiser, Ralf I.
中科院分区：
文献类型：
--
作者：
Yang, Zhenghai;Doddipatla, Srinivas;He, Chao;Krasnoukhov, Vladislav S.;Azyazov, Valeriy N.;Mebel, Alexander M.;Kaiser, Ralf I.
通过基态甲基炔自由基（CH）与硅烷（SiH4）的双分子气相反应，在单碰撞条件下合成了硅烯分子（H2SiCH2; X1A1）。利用交叉分子束实验和高水平电子结构计算，在双重态表面上，通过甲基炔自由基无障碍插入硅氢键形成硅甲基（CH2SiH3; X2A ‘）配合物，然后氢迁移到甲基硅基自由基（SiH2CH3; X2A ’），开始了基本反应。硅甲基和甲基硅基中间体都经历单分子氢损失为硅烯（H2SiCH2; X1A1）。甲基炔与硅烷的基本反应的探索提供了一个独特的视角，在广泛未知的反应动力学和异构化过程的气相碳硅系统，这是明显不同于那些同价碳系统，从而有助于我们的知识在分子水平上的碳硅键偶联。
The silene molecule (H2SiCH2; X1A1) has been synthesized under single collision conditions via the bimolecular gas phase reaction of ground state methylidyne radicals (CH) with silane (SiH4). Exploiting crossed molecular beams experiments augmented by high‐level electronic structure calculations, the elementary reaction commenced on the doublet surface through a barrierless insertion of the methylidyne radical into a silicon‐hydrogen bond forming the silylmethyl (CH2SiH3; X2A′) complex followed by hydrogen migration to the methylsilyl radical (SiH2CH3; X2A′). Both silylmethyl and methylsilyl intermediates undergo unimolecular hydrogen loss to silene (H2SiCH2; X1A1). The exploration of the elementary reaction of methylidyne with silane delivers a unique view at the widely uncharted reaction dynamics and isomerization processes of the carbon–silicon system in the gas phase, which are noticeably different from those of the isovalent carbon system thus contributing to our knowledge on carbon silicon bond couplings at the molecular level.