Theoretical study of methyl hypoflourite (CH3OF) and related compounds

Abstract

The Gaussian‐2 (G2) theoretical procedure, based on ab initio molecular orbital theory, is used to calculate the energies of CH₃OF, CH₃OF⁺, and related compounds. In this study we have found methyl hypofluorite to have a trans C_s structure and to be stable with respect to loss of fluorine by 45.9 kcal/mol. The energies of fragmentation processes of methyl hypofluorite calculated from G2 theory are in agreement with those measured by Ruscic, Appelman, and Berkowitz [J. Chem. Phys. 9 5, XXX (1991)] and support their interpretation of the photoionization data. The theoretical enthalpy of formation ΔH⁰_f0(CH₃OF) of −21.0 kcal/mol is in agreement with the experimental value (≥−23.0±0.7 kcal/mol) derived from the photoionization data. The ordering of the O–F bond strengths in the series of molecules OF, HOF, and CH₃OF is OF>HOF>CH₃OF and the C–O bond strength is 6–8 kcal/mol weaker in methyl hypofluorite than in methanol.