Abstract
A series of ab initio computations have been performed to estimate the CCSD(T) complete basis set limit of the axial/equatorial energy difference for the chair conformation of 1-fluoro, 1-chloro, 1-methyl, 1-hydroxy, and 1-methoxysilacyclohexanes. The equatorial conformation is more stable than the axial by 0.21 kcal mol-1 for 1-methylsilacyclohexane, while the axial position is more stable for 1-fluoro, 1-chloro, and 1-methoxysilacyclohexane (by 0.09, 0.40, and 0.15 kcal mol-1, respectively). The axial and equatorial orientations of 1-hydroxysilacyclohexane are nearly electronically isoenergetic (equatorial favored by 0.03 kcal mol-1). Zero-point vibrational energy corrections have very little effect on the relative energies (less than 0.08 kcal mol-1). These results suggest the presence of an interesting stereo electronic effect, similar to the anomeric effect, in these silacyclohexanes even without an additional heteroatom, like O, in the ring. © 2007 Wiley Periodicals, Inc.
Recommended Citation
A. J. Weldon and G. S. Tschumper, "Intrinsic Conformational Preferences of and an Anomeric-Like Effect in 1-Substituted Silacyclohexanes," International Journal of Quantum Chemistry, vol. 107, no. 12, pp. 2261 - 2265, Wiley, Oct 2007.
The definitive version is available at https://doi.org/10.1002/qua.21336
Department(s)
Chemistry
Publication Status
Full Access
Keywords and Phrases
Anomeric effect; Axial/ equatorial energy differences; CBS limit; Conformational analysis; Silacyclohexane compounds
International Standard Serial Number (ISSN)
1097-461X; 0020-7608
Document Type
Article - Conference proceedings
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2024 Wiley, All rights reserved.
Publication Date
01 Oct 2007
