Conformational analysis of N‐phenyl‐ and N‐trifyl‐4,4‐dimethyl‐4‐silathiane 1‐sulfimides |
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Authors: | Bagrat A. Shainyan Elena N. Suslova Erich Kleinpeter |
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Affiliation: | 1. A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Science,1 Favorsky Street, Irkutsk 664033, Russian Federation;2. Chemisches Institut der Universitat Potsdam, Karl‐Liebknecht‐Str. 24‐25, D‐14476 Potsdam (Golm), Germany |
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Abstract: | N‐Substituted 4,4‐dimethyl‐4‐silathiane 1‐sulfimides [R = Ph ( 1 ), CF3 ( 2 )] were studied experimentally by variable temperature dynamic NMR spectroscopy. Low temperature 13C NMR spectra of the two compounds revealed the frozen ring inversion process and approximately equal content of the axial and equatorial conformers. Calculations of the 4‐silathiane derivatives 1 , 2 and the model compound [R = Me ( 3 )] as well as their carbon analogs, the similarly N‐substituted thiane 1‐sulfimides [R = Ph ( 4 ), CF3 ( 5 ), Me ( 6 )] at the DFT/B3LYP/6–311G(d,p) level in the gas phase and in chloroform solution using the PCM model at the same level of theory showed a strong dependence of the relative stability of the conformer on the solvent. The electronegative trifluoromethyl group increases the relative stability of the axial conformer. Copyright © 2010 John Wiley & Sons, Ltd. |
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Keywords: | 4‐silathianes conformational analysis dynamic NMR quantum chemical calculations sulfimides |
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