Journal of Physical Chemistry A, Vol.101, No.15, 2906-2909, 1997
Computational Study of C-H Bond Strengths in Polyfluoroalkanes
Ab initio energies obtained at the MP2/6-311 +G(3df,2p)//MP2/6-31G(d) level of theory have been employed in isodesmic reactions to obtain C-H bond dissociation enthalpies at 298 K for a variety of C-1-C-4 hydrofluorocarbons. There is good accord with the experimental data that are available for C-1 and C-2 species. Several relations between structure and BDE have been noted, and trends where -H and/or -CH3 groups are replaced by -F and/or -CF3 were rationalized in terms of the inductive effect, involving sigma and/or pi electron donation and withdrawal. The strongest predicted C-H bonds are (CF3)(3)C-H and (CF3)(2)CH-H, both with BDEs of 450 kJ/mol, which are up to about 45 kJ/mol higher than the hydrocarbon analogs.
Keywords:VIBRATIONAL FREQUENCIES;THERMODYNAMIC FUNCTIONS;INTERNAL-ROTATION;BARRIERS;RADICALS;ABINITIO;ENERGIES;INVERSION