1-Methylthio-1-phenyl-1-silacyclohexane: Synthesis,conformational preferences in gas and solution by GED,NMR and theoretical calculations |
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| Institution: | 1. School of Mathematics and Physics, Beijing Key Laboratory for Magneto-Photoelectrical Composite and Interface Science, University of Science and Technology Beijing, Beijing 100083, PR China;2. School of Information Science and Engineering, Lanzhou University, Lanzhou 731100, PR China;3. Computational Center for Property and Modification on Nanomaterials, College of Science, Liaoning Shihua University, Fushun 113001, PR China |
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| Abstract: | 1-Methylthio-1-phenyl-1-silacyclohexane 1, the first silacyclohexane with the sulfur atom at silicon, was synthesized and its molecular structure and conformational preferences studied by gas-phase electron diffraction (GED) and low temperature 13C and 29Si NMR spectroscopy (LT NMR). Quantum-chemical calculations were carried out both for the isolated species and solvate complexes in gas and in polar medium. The predominance of the 1-MeSaxPheq conformer in gas phase (1-Pheq:1-Phax = 55:45, ΔG° = 0.13 kcal/mol) determined from GED is consistent with that measured in the freon solution by LT NMR (1-Pheq:1-Phax = 65:35, ΔG° = 0.12 kcal/mol), the experimentally measured ratios being close to that estimated by quantum chemical calculations at both the DFT and MP2 levels of theory. |
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| Keywords: | 1-Methylthio-1-phenyl-1-silacyclohexane Conformational analysis Gas phase electron diffraction DFT and MP2 calculations |
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