Combined Experimental and Theoretical Study on the Formation of the Elusive 2-Methyl-1-silacycloprop-2-enylidene Molecule under Single Collision Conditions via Reactions of the Silylidyne Radical (SiH

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• 作者：Tao Yang ; Beni B. Dangi ; Pavlo Maksyutenko ; Ralf I. Kaiser Luke W. Bertels ; Martin Head-Gordon
• 刊名：Journal of Physical Chemistry A
• 出版年：2015
• 出版时间：December 17, 2015
• 年：2015
• 卷：119
• 期：50
• 页码：12562-12578
• 全文大小：866K
• ISSN：1520-5215

文摘

The crossed molecular beam reactions of the ground-state silylidyne radical (SiH; X²螤) with allene (H₂CCCH₂; X¹A₁) and D4-allene (D₂CCCD₂; X¹A₁) were carried out at collision energies of 30 kJ mol^鈥?. Electronic structure calculations propose that the reaction of silylidyne with allene has no entrance barrier and is initiated by silylidyne addition to the 蟺 electron density of allene either to one carbon atom (C1/C2) or to both carbon atoms simultaneously via indirect (complex forming) reaction dynamics. The initially formed addition complexes isomerize via two distinct reaction pathways, both leading eventually to a cyclic SiC₃H₅ intermediate. The latter decomposes through a loose exit transition state via an atomic hydrogen loss perpendicularly to the plane of the decomposing complex (sideways scattering) in an overall exoergic reaction (experimentally: 鈭?9 卤 13 kJ mol^鈥?; computationally: 鈭? 卤 3 kJ mol^鈥?). This hydrogen loss yields the hitherto elusive 2-methyl-1-silacycloprop-2-enylidene molecule (c-SiC₃H₄), which can be derived from the closed-shell cyclopropenylidene molecule (c-C₃H₂) by replacing a hydrogen atom with a methyl group and the carbene carbon atom by the isovalent silicon atom. The synthesis of the 2-methyl-1-silacycloprop-2-enylidene molecule in the bimolecular gas-phase reaction of silylidyne with allene enriches our understanding toward the formation of organosilicon species in the gas phase of the interstellar medium in particular via exoergic reactions of no entrance barrier. This facile route to 2-methyl-1-silacycloprop-2-enylidene via a silylidyne radical reaction with allene opens up a versatile approach to form hitherto poorly characterized silicon-bearing species in extraterrestrial environments; this reaction class might represent the missing link, leading from silicon-bearing radicals via organosilicon chemistry eventually to silicon鈥揷arbon-rich interstellar grains even in cold molecular clouds where temperatures are as low as 10 K.