Infrared and Raman spectra, conformational stability, normal coordinate analysis, ab initio calculations, and vibrational assignment of 1-fluoro-1-methylsilacyclobutane

Abstract

The infrared (3500–40 cm −1) spectra of gaseous and solid 1-fluoro-1-methylsilacyclobutane, c-C 3H 6SiF(CH 3), have been recorded. Additionally, the Raman spectrum (3500–30 cm −1) of the liquid has been recorded and quantitative depolarization values have been obtained. Both the axial and equatorial (with respect to the methyl group) conformers have been identified in the fluid phases. Variable temperature (−55–−100°C) studies of the infrared spectra of the sample dissolved in liquid xenon have been carried out. From these data, the enthalpy difference has been determined to be 267±10 cm −1 (3.19±0.12 kJ mol −1), with the axial conformer being the more stable form and the only conformer remaining in the polycrystalline solid. A complete vibrational assignment is proposed for the axial conformer and many of the fundamentals for the equatorial conformer have also been identified. The vibrational assignments are supported by normal coordinate calculations utilizing ab initio force constants. Complete equilibrium geometries have been determined for both rotamers by ab initio calculations employing the 6-31G* and 6-311++G** basis sets at the levels of restricted Hartree–Fock (RHF) and/or Moller–Plesset (MP) to second order. The results are discussed and compared to those obtained for some similar molecules.