Conformational stabilities and structural parameters of (CH 3) nCH 3− n CFO molecules

Abstract

Variable temperature (−60 to −100 °C) studies of the infrared spectra (3500–400 cm −1) of propionyl fluoride (CH 3CH 2CFO) and 2-methylpropionyl fluoride ((CH 3) 2CHCFO), dissolved in liquid xenon have been recorded. From these data, the enthalpy difference has been determined to be 329±33 cm −1 (3.94±0.39 kJ/mol) for propionyl fluoride with the trans conformer (methyl group eclipsing the oxygen atom) more stable than the gauche form. For 2-methylpropionyl fluoride, the enthalpy difference has been determined to be 297±30 cm −1 (3.55±0.36 kJ/mol) with the gauche conformer (methyl group eclipsing the oxygen atom) more stable than the trans form. From these Δ H values along with assigned torsional fundamentals for both conformers and accompanying “hot bands” the potential functions governing the conformational interchange have been calculated. Utilizing the infrared data from the xenon solution and ab initio frequency predictions from MP2/6-31G * calculations, a few reassignments of the fundamentals have been made. Ab initio calculations have been carried out with several different basis sets up to MP2/6-311+G ** from which structural parameters and conformational stabilities have been determined. Additionally, force constants, infrared intensities, Raman activities, depolarization ratios, and scaled vibrational frequencies have been determined from MP2/6-31G * calculations. Adjusted structural parameters have been obtained from combined ab initio predicted values and previously reported microwave data. These parameters are compared to those obtained from either the earlier microwave and/or electron diffraction studies. Similar ab initio calculations and structural parameter determinations have been carried out for acetyl fluoride (CH 3CFO) and trimethylacetyl fluoride ((CH 3) 3CCFO) and compared to the corresponding experimental results when appropriate.