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.
Author details: | Bagrat A. Shainyan, Elena N. Suslova, Erich KleinpeterORCiDGND |
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DOI: | https://doi.org/10.1002/poc.1811 |
ISSN: | 0894-3230 |
Title of parent work (English): | Journal of physical organic chemistry |
Publisher: | Wiley-Blackwell |
Place of publishing: | Malden |
Publication type: | Article |
Language: | English |
Year of first publication: | 2011 |
Publication year: | 2011 |
Release date: | 2017/03/26 |
Tag: | 4-silathianes; conformational analysis; dynamic NMR; quantum chemical calculations; sulfimides |
Volume: | 24 |
Issue: | 8 |
Number of pages: | 7 |
First page: | 698 |
Last Page: | 704 |
Funding institution: | Russian Foundation for Basic Research [08-03-91954]; Deutsche Forschungsgemeinschaft [08-03-91954] |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer review: | Referiert |