Conformational Stability of Propenoyl Bromide from Temperature-Dependent Infrared Spectra of Krypton Solutions, Ab Initio Calculations, and r0 Structural Parameters of the Propenoyl Halides (F, Cl, Br)

Variable temperature (−100 to −150°C) studies of the infrared spectra (3500–400 cm−1) of propenoyl bromide, CH2=CHCBrO, dissolved in liquid krypton, have been carried out. Utilizing six different conformer pairs, an enthalpy difference of 204 ± 20 cm−1 (2.44 ± 0.24 kJ/mol) was obtained, with the anti conformer (carbonyl bond trans to C=C bond) the more stable form. At ambient temperature, there is approximately 28 ± 2% of the syn conformer present. The anti conformer also remains in the infrared and Raman spectra of the polycrystalline solid. The optimal geometries, conformational stabilities, harmonic force fields, infrared intensities, Raman activities, depolarization ratios, and vibrational frequencies, are reported for both conformers from MP2/6-31G(d) ab initio calculations. The potential function governing the conformational interchange has been obtained from the MP2/6-31G(d) ab initio calculations. The conformational stabilities were calculated from a variety of basis sets and at the highest level of calculations, MP2/6-311 + (2df,2pd), the anti conformer is predicted to be more stable by 178 cm−1, which is in excellent agreement with the experimental results. The r0 adjusted structural parameters have been obtained for propenoyl fluoride and chloride from a combination of the previously reported microwave rotational constants and ab initio predicted parameters. Several of the parameters for the chloride are significantly different than those proposed from an electron diffraction investigation. The results of these spectroscopic, structural, and theoretical studies are discussed and compared to the corresponding results for some similar molecules.