Conformational stability, r0 structural parameters, and vibrational assignments of mono-substituted cyclobutanes: Fluorocyclobutane

Abstract

Variable temperature (−55 to −100 °C) studies of the infrared spectra (3500–400 cm −1) of fluorocyclobutane, c-C 4H 7F, dissolved in liquid xenon have been carried out as well as the infrared spectra of the gas. By utilizing eight pairs of conformers at 10 different temperatures, the enthalpy difference between the more stable equatorial conformer and the axial form has been determined to be 496 ± 40 cm −1 (5.93 ± 0.48 kJ/mol). The percentage of the axial conformer present at ambient temperature is estimated to be 8 ± 1%. The ab initio MP2(full) average predicted energy difference from a variety of basis sets is 732 ± 47 cm −1 (9.04 ± 0.44 kJ/mol) and the average value of 602 ± 20 cm −1 from density functional theory predictions by the B3LYP method are significantly larger than the experimentally determined enthalpy value. By utilizing previously reported microwave rotational constants for the equatorial and axial conformers combined with ab initio MP2(full)/6-311+G(d,p) predicted structural values, adjusted r 0 parameters have been obtained. The determined heavy atom structural parameters for the equatorial [axial] conformer are: distances (Å) C–F = 1.383(3) [1.407(3)], C α–C β = 1.543(3) [1.546(3)], C β–C γ = 1.554(3) [1.554(3)] and angles (°) ∠C αC βC γ = 85.0(5) [89.2(5)], ∠C βC αC β = 89.3(5) [89.2(5)], ∠F–(C βC αC β) = 117.4(5) [109.2(5)] and a puckering angle of 37.4(5) [20.7(5)]. The conformational stabilities, harmonic force fields, infrared intensities, Raman activities, depolarization ratios and vibrational frequencies have been obtained for both conformers from MP2(full)/6-31G(d) ab initio calculations and compared to experimental values where available. The results are discussed and compared to the corresponding properties of some other monosubstituted cyclobutanes with halogen and pseudo-halogen substituents.