Conformational analysis of N-phenyl- and N-trifyl-4,4-dimethyl-4-silathiane 1-sulfimides
- N-Substituted 4,4-dimethyl-4-silathiane 1-sulfimides Me2Si(sic)S=NSO2R [R- Ph (1), CF3 (2)] were studied experimentally by variable temperature dynamic NMR spectroscopy. Low temperature 13 C 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 (sic)S=NSO2R 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.
Verfasserangaben: | Bagrat A. Shainyan, Elena N. Suslova, Erich KleinpeterORCiDGND |
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DOI: | https://doi.org/10.1002/poc.1811 |
ISSN: | 0894-3230 |
Titel des übergeordneten Werks (Englisch): | Journal of physical organic chemistry |
Verlag: | Wiley-Blackwell |
Verlagsort: | Malden |
Publikationstyp: | Wissenschaftlicher Artikel |
Sprache: | Englisch |
Jahr der Erstveröffentlichung: | 2011 |
Erscheinungsjahr: | 2011 |
Datum der Freischaltung: | 26.03.2017 |
Freies Schlagwort / Tag: | 4-silathianes; conformational analysis; dynamic NMR; quantum chemical calculations; sulfimides |
Band: | 24 |
Ausgabe: | 8 |
Seitenanzahl: | 7 |
Erste Seite: | 698 |
Letzte Seite: | 704 |
Fördernde Institution: | Russian Foundation for Basic Research [08-03-91954]; Deutsche Forschungsgemeinschaft [08-03-91954] |
Organisationseinheiten: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer Review: | Referiert |