Negrebetsky, Vadim V.; Taylor, Peter G.; Kramarova, Evgeniya P.; Shipov, Aleksander G.; Pogozhikh, Sergey A.; Ovchinnikov, Yuri E.; Korlyukov, Alexander A.; Bowden, Allen; Bassindale, Alan R. and Baukov, Yuri I.
|DOI (Digital Object Identifier) Link:||http://doi.org/10.1016/j.jorganchem.2008.01.033|
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The novel compounds, N-(trifluorosilylmethyl)-[N-(S)-(1-phenylethyl)]-acetamide (1a) and 1-(trifluorosilylmethyl)-2-oxoperhydroazepine (1b) have been prepared from the corresponding NH-compounds using ClCH2SiCl3/Et3N or ClCH2SiCl3/(Me3Si)2NH followed by methanolysis or hydrolysis of the reaction mixture in the presence of Lewis bases, and then BF3 etherate. Potassium-(18-crown-6)-(2-oxoperhydroazepinomethyl)tetrafluorosilicate (2) was synthesized by reaction of the trifluoride (1b) with KF in the presence of 18-crown-6. Using 19F, 29Si NMR and X-ray diffraction techniques it was established that the silicon atom is pentacoordinate in the trifluorides (1a, b) and hexacoordinate in the adduct 2. Thus the internal coordination of the O → Si bond present in the trifluoride (1b) is retained in the adduct 2.
The stereochemical non-rigidity of the trifluorides (1a, b) and the N-(trifluorosilylmethyl)-N-methylacetamide (1c) was investigated using dynamic 19F NMR spectroscopy. The activation barriers for permutational isomerization are in the range 9.5–10 kcal mol−1. Lower values of ΔG# for permutation of trifluorides (1a–c) compared to the monofluorides with the coordination core OSiC3F together with small negative values for the activation entropy implies a non-dissociative mechanism. Quantum-chemical analysis suggests a mechanism involving a turnstile rotation.
|Item Type:||Journal Article|
|Copyright Holders:||2008 Elsevier|
|Keywords:||Pentacoordination; Hexacoordination; X-ray diffraction study; Stereochemical non-rigidity; Dynamic NMR; Quantum-chemical calculations|
|Academic Unit/Department:||Faculty of Science, Technology, Engineering and Mathematics (STEM) > Life, Health and Chemical Sciences
Faculty of Science, Technology, Engineering and Mathematics (STEM)
Other Departments > Vice-Chancellor's Office
|Interdisciplinary Research Centre:||Biomedical Research Network (BRN)
Centre for Earth, Planetary, Space and Astronomical Research (CEPSAR)
|Depositing User:||Peter Taylor|
|Date Deposited:||28 Dec 2010 15:10|
|Last Modified:||04 Oct 2016 10:53|
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