Weak, improper, C-O...H-C hydrogen bonds in the dimethyl ether dimer

Yoshio Tatamitani; Bingxin Liu; Jun Shimada; Teruhiko Ogata; Paolo Ottaviani; Assimo Maris; Walther Caminati; José L Alonso

doi:10.1021/ja0164069

Weak, improper, C-O...H-C hydrogen bonds in the dimethyl ether dimer

J Am Chem Soc. 2002 Mar 20;124(11):2739-43. doi: 10.1021/ja0164069.

Authors

Yoshio Tatamitani¹, Bingxin Liu, Jun Shimada, Teruhiko Ogata, Paolo Ottaviani, Assimo Maris, Walther Caminati, José L Alonso

Affiliation

¹ Department of Chemistry, Faculty of Science, Shizuoka University, Ohya, Shizuoka 422-8529 Japan.

PMID: 11890825
DOI: 10.1021/ja0164069

Abstract

The ground-state rotational spectrum of the dimethyl ether dimer, (DME)(2), has been studied by molecular beam Fourier transform microwave and free jet millimeter wave absorption spectroscopies. The molecular beam Fourier transform microwave spectra of the (DME-d(6))(2), (DME-(13)C)(2), (DME-d(6))...(DME), (DME-(13)C)...(DME), and (DME)...(DME-(13)C) isotopomers have also been assigned. The rotational parameters have been interpreted in terms of a C(s) geometry with the two monomers bound by three weak C-H...O hydrogen bonds, each with an average interaction energy of about 1.9 kJ/mol. The experimental data combined with high-level ab initio calculations show this kind of interaction to be improper, blue-shifted hydrogen bonding, with an average shortening of the C-H bonds involved in the hydrogen bonding of 0.0014 A. The length of the C-H...O hydrogen bonds, r(O...H), is in the range 2.52-2.59 A.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Dimerization
Fourier Analysis
Hydrogen Bonding
Methyl Ethers / chemistry*
Microwaves
Molecular Conformation
Spectrum Analysis / methods

Substances

Methyl Ethers
dimethyl ether