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Conformational properties of 1-tert-butyl-1-silacyclohexane, C5H10SiH(t-Bu): gas-phase electron diffraction, temperature-dependent Raman spectroscopy, and quantum chemical calculations

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Abstract

The conformational preference of the t-butyl group in 1-t-Bu-1-silacyclohexane was studied experimentally by means of gas-phase electron diffraction (GED), and temperature-dependent Raman spectroscopy as well as by quantum chemical calculations applying density functional theory and ab initio methods. According to the GED experiment at 283 K, the vapor of the title compound contains only the equatorial conformer. At 99.5 % level of confidence, up to 4 % of axial conformer cannot be completely excluded, however. The Raman spectroscopy experiment in the temperature range of 295–375 K of the neat liquid indicated that the equatorial conformer is favored over the axial one by 0.56 (15) kcal mol−1 (ΔH values). The experimental values are fairly well reproduced by the calculations. CCSD(T) calculations predict the equatorial conformer to have a 1.19 kcal mol−1 lower Gibbs free energy (corresponding to about 89 % equatorial preference) and a 0.99 kcal mol−1 lower enthalpy than the axial conformer at 300 K. According to natural bond orbital analysis, the equatorial conformer of the title compound is an example of a molecular stabilization, which is not favored by steric and conjugation effects but favored by electrostatic interactions. Results from dynamic NMR experiments were inconclusive.

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Acknowledgments

A financial support from RANNÍS—The Icelandic Centre for Research (Grant No. 080038021) is gratefully acknowledged. A.V.B. is grateful to the Government of RF (Project 11.G34.31.0069). S.A.S. is grateful to the Russian Foundation for Basic Research, RFBR (Grant No. 14-03-00923-a). T.K. and K.H. thank the Austrian Science Foundation FWF (Fonds zur Förderung der wissenschaftlichen Forschung, Vienna) for financial support of project P 21272-N19.

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Author notes

  1. Sunna Ó. Wallevik

    Present address: ICI Rheocenter, Innovation Center Iceland, Reykjavik University, 112, Reykjavík, Iceland

  2. Thomas Kern

    Present address: Takeda Austria GmbH, St. Peter-Straße 25, 4020, Linz, Austria

Authors and Affiliations

  1. Saint-Petersburg State Technological Institute, Saint Petersburg, 190013, Russia

    Alexander V. Belyakov & Yurii Sigolaev

  2. Ivanovo State University of Chemistry and Technology, Sheremetevskiy Ave. 7, 153000, Ivanovo, Russia

    Sergey A. Shlykov

  3. Science Institute, University of Iceland, Dunhaga 3, 107, Reykjavík, Iceland

    Sunna Ó. Wallevik, Nanna R. Jonsdottir, Ragnar Bjornsson, Sigridur Jonsdottir, Ágúst Kvaran & Ingvar Arnason

  4. Technische Universität Graz, Stremayergasse 16, 8010, Graz, Austria

    Thomas Kern & Karl Hassler

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  1. Alexander V. Belyakov
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Corresponding author

Correspondence to Ingvar Arnason.

Electronic supplementary material

11224_2014_503_MOESM1_ESM.docx

Van´t Hoff plots using relative band heights and band areas, respectively. MP2-cc-pVTZ optimized geometries. Supplementary material 1 (DOCX 134 kb)

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Belyakov, A.V., Sigolaev, Y., Shlykov, S.A. et al. Conformational properties of 1-tert-butyl-1-silacyclohexane, C5H10SiH(t-Bu): gas-phase electron diffraction, temperature-dependent Raman spectroscopy, and quantum chemical calculations. Struct Chem 26, 445–453 (2015). https://doi.org/10.1007/s11224-014-0503-6

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