Abstract
Infrared and Raman spectra are reported for CH 3OCH 2X, CHD 2OCD 2X, CD 3OCHDX (XF, Cl, Br, I) and for CH 3OCD 2Cl and CD 3OCH 2Cl, in various phases. ν CH is values are obtained which enable CH bond lengths and dissociation energies to be predicted. The changes in bond lengths from Me 2O to MeOCH 2X and from MeOCH 2F to MeOCH 2Cl are in good agreement with those calculated ab initio and in radical disagreement with microwave-based values. The effect of halogen is to strengthen all the CH bonds present, especially that lying parallel to the CX one. All major features in the spectra are explained if only the gauche skeletal conformer exists in the phases studied. However, two transient bands in solid films of CH 3OCH 2F may indicate the presence of a metastable trans conformer phase. Secure assignments for CH 3OCH 2Cl are based on the CH 3OCD 2Cl and CD 3OCH 2Cl spectra and extended by analogy to most of the vibrations of the F, Br and I compounds.
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