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- Title
Conformational energies of silacyclohexanes C<sub>5</sub>H<sub>10</sub>SiHMe, C<sub>5</sub>H<sub>10</sub>SiH(CF<sub>3</sub>) and C<sub>5</sub>H<sub>10</sub>SiCl(SiCl<sub>3</sub>) from variable temperature Raman spectra.
- Authors
Kern, Thomas; Hölbling, Margit; Dzambaski, Ana; Flock, Michaela; Hassler, Karl; Wallevik, Sunna Ó.; Arnason, Ingvar; Bjornsson, Ragnar
- Abstract
From variable temperature vibrational Raman spectra, the axial/equatorial enthalpy differences for the substituted silacyclohexanes C5H10SiHMe, C5H10SiH(CF3) and C5H10SiCl(SiCl3) were determined. The pure liquids and solutions in various solvents were investigated. Preferred conformations are equatorial for methylsilacyclohexane and axial for trifluoromethylsilacyclohexane, consistent with earlier results from nuclear magnetic resonance experiments and ab initio calculations. For C5H10SiCl(SiCl3) an enthalpy difference close to zero was found, which is supported by high-level which is supported by high-level quantum chemical calculations at the second-order Møller-Plesset (MP2) and coupled cluster with single, double, and perturbative triple excitations (CCSD(T)) levels, which employed various basis sets. A novel synthesis for C5H10SiCl(SiCl3) was developed using ClMg(CH2)5MgCl instead of BrMg(CH2)5MgBr as a starting material. The procedure avoids the formation of partially brominated products, facilitating the purification of the compound. 1H, 13C and 29Si nuclear magnetic resonance data are reported. Copyright © 2012 John Wiley & Sons, Ltd.
- Subjects
CYCLOHEXANE; RAMAN spectra; ENTHALPY; SOLVENT analysis; TRIFLUOROMETHYL compounds; NUCLEAR magnetic resonance
- Publication
Journal of Raman Spectroscopy, 2012, Vol 43, Issue 9, p1337
- ISSN
0377-0486
- Publication type
Article
- DOI
10.1002/jrs.3164