Conformational Analysis of (1,1′-Phenyl-1,1′-silacyclohex-1-yl)disiloxane. DFT and Low-Temperature 13C NMR Spectroscopy Study
- Autores: Shainyan B.1, Kleinpeter E.2, Suslova E.1
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Afiliações:
- I.A. Favorskii Institute of Chemistry
- Institute of Chemistry
- Edição: Volume 89, Nº 4 (2019)
- Páginas: 713-716
- Seção: Article
- URL: https://journals.rcsi.science/1070-3632/article/view/222855
- DOI: https://doi.org/10.1134/S1070363219040121
- ID: 222855
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Resumo
The DFT and MP2 theoretical conformational analysis of the recently synthesized (1,1′-phenyl-1,1′-silacyclohex-1-yl)disiloxane has revealed the energetic preference of the Phax,Phax conformer. The Phax,Phax: Phax,Pheq: Pheq,Pheq conformers ratio has been estimated as of 46.6: 33.1: 20.3 from the M062X/6-311G(d,p) free energy simulation, suggesting the possibility of detecting individual conformers experimentally, e.g., by low-temperature 1H and 13C NMR spectroscopy. However, only the presence of several conformers has been detected by means of 1H NMR spectroscopy at 113 K; determination of the Δν (Hz) and ΔG# (kcal/mol) parameters for the 6-membered ring interconversion has been impossible due to the signals broadening at low temperature, signal temperature shifts, and extremely low barrier of ring inversion at Tc < 113 K.
Sobre autores
B. Shainyan
I.A. Favorskii Institute of Chemistry
Autor responsável pela correspondência
Email: bagrat@irioch.irk.ru
Rússia, ul. Favorskogo 1, Irkutsk, 664033
E. Kleinpeter
Institute of Chemistry
Email: bagrat@irioch.irk.ru
Alemanha, Potsdam
E. Suslova
I.A. Favorskii Institute of Chemistry
Email: bagrat@irioch.irk.ru
Rússia, ul. Favorskogo 1, Irkutsk, 664033
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