Please use this identifier to cite or link to this item: https://doi.org/10.1021/jp035300s
Title: Gaunche/trans equilibria of 2,2′-Bi-1,3-dioxanyl, 2,2′-dimethyl-2,2′-bi-1,3-dioxanyl,2,2′-Bi-1,3-dithianyl, and 2,2′-dimethyl-2,2′-bi-1,3-dithianyl in different media. Theory and experiment
Authors: Chen, W.
Lam, Y. 
Wong, M.W. 
Huang, H.H. 
Liang, E.
Issue Date: 28-Aug-2003
Citation: Chen, W., Lam, Y., Wong, M.W., Huang, H.H., Liang, E. (2003-08-28). Gaunche/trans equilibria of 2,2′-Bi-1,3-dioxanyl, 2,2′-dimethyl-2,2′-bi-1,3-dioxanyl,2,2′-Bi-1,3-dithianyl, and 2,2′-dimethyl-2,2′-bi-1,3-dithianyl in different media. Theory and experiment. Journal of Physical Chemistry A 107 (34) : 6714-6719. ScholarBank@NUS Repository. https://doi.org/10.1021/jp035300s
Abstract: The gauche/trans conformational equilibria of 2,2′-bi-1,3-dioxanyl (1), 2,2′-dimethyl-2,2′-bi-1,3-dioxanyl (2), 2,2′-bi-1,3-dithianyl (3), and 2,2′-dimethyl-2,2′-bi-1,3-dithianyl (4) dissolved in carbon tetrachloride and benzene are studied through dipole moment determination. Analyses of the relative permittivity data show that the dioxa system favors the trans form at 25°C. Replacement of the oxygen atoms in 1 with sulfur completely reverses the gauche/trans equilibrium in carbon tetrachloride such that 3 exists predominantly in the gauche form. However, 4 exists mainly in the trans conformation in carbon tetrachloride solution and both 3 and 4 favor the trans form in benzene. X-ray crystallographic determination revealed that 1-4 favored the trans conformation in the solid state. Ab initio and DFT calculations were performed to examine the structural features of 1-4 and study the effects of solvent on these molecules. The calculated gauche/trans equilibria of 3 in different media are in excellent accord with the experimental findings. The observed difference in conformational preference of 3 in CCl4 and benzene can be explained in terms of the specific solvation effect of benzene. CH⋯X (X = O or S) are important to understand the structures and relative energies of these 1,3-diheteroane systems.
Source Title: Journal of Physical Chemistry A
URI: http://scholarbank.nus.edu.sg/handle/10635/93881
ISSN: 10895639
DOI: 10.1021/jp035300s
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

SCOPUSTM   
Citations

4
checked on Aug 15, 2018

WEB OF SCIENCETM
Citations

4
checked on Jul 23, 2018

Page view(s)

32
checked on Aug 3, 2018

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.