Theoretical Studies of SiC4H2 Isomers Delineate Three Low-Lying Silylidenes Are Missing in the Laboratory

J Phys Chem A. 2020 Feb 6;124(5):987-1002. doi: 10.1021/acs.jpca.9b11742. Epub 2020 Jan 23.

Abstract

Eleven isomers of SiC4H2 lying within 50 kcal mol-1 have been theoretically investigated using density functional theory and high-level coupled-cluster methods. Among them, four isomers, 1-ethynyl-3-silacycloprop-1(2)-en-3-ylidene (1), diethynylsilylidene (2), 1-sila-1,2,3,4-pentatetraenylidene (4), and 1,3-butadiynylsilylidene (5), have already been identified in the laboratory. The current investigation reports three low-lying (<1 eV) silylidenes [2-methylenesilabicyclo[1.1.0]but-1(3)-en-4-ylidene (3), 4-sila-2-methylenebicyclo[1.1.0]but-1(3)-en-4-ylidene (6), and 3-ethynyl-1-silapropadienylidene (7)] and three high-lying (>1 eV) silylidenes [2-sila-(didehydrovinylidene)cyclopropene (8), an isomer with a planar tetracoordinate carbon (ptC) atom (10), and 1-ethynyl-1-silapropadienylidene (11)], which remain elusive in the laboratory to date. Isomer 9 also contains a ptC atom, which turned out to be a transition state at all levels. Though all isomers are polar (μ ≠ 0), rotational spectrum is available only for 4. Using matrix isolation, three isomers (1, 2, and 5) have been trapped in the laboratory at 10 K. Considering the astrochemical relevance of silicon-carbide clusters in the interstellar medium, the current theoretical data demand new molecular spectroscopic studies on SiC4H2. Surprisingly, unlike the isovalent C5H2 isomers, where the bent carbenes are yet to be identified in the laboratory, the bent silylidenes (2 and 5) have been trapped in the case of SiC4H2. In both the cases, molecules with transannular C-C and/or Si-C bonds remain elusive, though they lie in the low-lying region. Using suitable precursors, whether these peculiar geometries (especially 3 and 6) would be identified or not in the laboratory needs to be addressed by molecular spectroscopists. The present investigation documents structural and spectroscopic information of SiC4H2 isomers, which may compliment future molecular spectroscopic observations including radioastronomical searches.