Structural Study and Conformational-Analysis of T-Butyl Ethyl Ether by Gas Electron-Diffraction, Ab-Initio Calculations and Vibrational Spectroscopy

by Egawa, T.; Moriyama, H.; Takeuchi, H.; Konaka, S.; Siam, K.; Schafer, L.

The molecular structure and conformational properties of t-butyl ethyl ether were studied by gas electron diffraction. Structural constraints of the data analysis were obtained from HF/4-21G ab initio geometry optimizations, and mean amplitudes of vibration and shrinkage corrections were calculated from vibrational spectra recorded for this analysis. At room temperature the compound exists in a conformational equilibrium of two forms, trans and skew, in a ratio of 70: 30 +/- 24%. Subject to the constraints of the analysis, the following structural parameters were found for the trans conformer: r(g)(O-C)t-Bu = 1.436(3) angstrom; r(g)(O-C)t-Bu - r(g)(O-C)Et = 0.014 angstrom (assumed); r(g)(C-C)t-Bu = 1.532(2) angstrom (averaged value); r(g)(C-C)t-Bu - r(g)(C-C)Et = 0.008 angstrom (assumed); r(g)(C-H) = 1.121(3) angstrom; angle(alpha) C-O-C = 119.9(12)-degrees; angle(alpha)C-C-C(t-Bu) = 111.1 (5)-degrees; angle(alpha)0-C-C(Et) = 109.3(15)-degrees; the tilt angle of the t-butyl group T(alpha) = 4.5(8)-degrees. Parenthesized values are error estimates (3sigma) referring to the last significant digit. The effects of steric repulsion on the structural parameters are discussed.

Journal
Journal of Molecular Structure
Volume
298
Year
1993
Start Page
37-45
URL
https://dx.doi.org/10.1016/0022-2860(93)80205-a
ISBN/ISSN
1872-8014; 0022-2860
DOI
10.1016/0022-2860(93)80205-a