A new method for estimation of homolytic C-H bond dissociation enthalpies
In this work we have quantitatively analyzed substituent effects on the homolytic bond dissociation enthalpy of 79 different compounds using a method based on discrete distance dependent atomic contributions to a molecular property. The resulting empirical relationship can be used to predict C-H bond dissociation enthalpies (within +/-10 kJ mol(-1)) for molecules where resonance contributions and captodative stabilization are insignificant. For species where captodative stabilization of the corresponding C-centered radical is possible, the method clearly overestimates the C-H bond dissociation enthalpy.
Cherkasov
A
Department of Chemistry, Nuclear Chemistry, Royal Institute of Technology, Stockholm, Sweden.
Jonsson
M