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: https://doi.org/10.1016/j.jorganchem.2008.01.033

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.

Viewing alternatives

Metrics

Item Actions

Export

You can export this page using these formats Digital Object Identifier - DOI

About

• Item ORO ID
• 25703
• Item Type
• Journal Item
• ISSN
• 0022-328X
• Keywords
• Pentacoordination; Hexacoordination; X-ray diffraction study; Stereochemical non-rigidity; Dynamic NMR; Quantum-chemical calculations
• Academic Unit or School
• 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
  Other Departments
• Copyright Holders
• © 2008 Elsevier
• Depositing User
• Peter Taylor