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Synthesis, structure and dynamic stereochemistry of (O→Si)-chelate N-(trifluorosilylmethyl)-[N-(S)-(1-phenylethyl)]acetamide and 1-(trifluorosilylmethyl)-2-oxoperhydroazepine: Retention of the O→Si coordination in the adduct with KF and 18-crown-6

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. (2008). Synthesis, structure and dynamic stereochemistry of (O→Si)-chelate N-(trifluorosilylmethyl)-[N-(S)-(1-phenylethyl)]acetamide and 1-(trifluorosilylmethyl)-2-oxoperhydroazepine: Retention of the O→Si coordination in the adduct with KF and 18-crown-6. Journal of Organometallic Chemistry, 693(7) pp. 1309–1320.

DOI (Digital Object Identifier) Link: http://dx.doi.org/10.1016/j.jorganchem.2008.01.033
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Abstract

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
ISSN: 0022-328X
Keywords: Pentacoordination; Hexacoordination; X-ray diffraction study; Stereochemical non-rigidity; Dynamic NMR; Quantum-chemical calculations
Academic Unit/Department: Science > Life, Health and Chemical Sciences
Science
Other Departments > Vice-Chancellor's Office
Interdisciplinary Research Centre: Biomedical Research Network (BRN)
Centre for Earth, Planetary, Space and Astronomical Research (CEPSAR)
Item ID: 25703
Depositing User: Peter Taylor
Date Deposited: 28 Dec 2010 15:10
Last Modified: 24 Nov 2014 12:13
URI: http://oro.open.ac.uk/id/eprint/25703
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