A new method for estimation of homolytic C-H bond dissociation enthalpies

In this work we have quantitatively analyzed substituent effects on the hom olytic bond dissociation enthalpy of 79 different compounds using a method based on discrete distance dependent atomic contributions to a molecular pr operty. The resulting empirical relationship can be used to predict C-H bon d dissociation enthalpies (within +/-10 kJ mol(-1)) for molecules where res onance contributions and captodative stabilization are insignificant. For s pecies where captodative stabilization of the corresponding C-centered radi cal is possible, the method clearly overestimates the C-H bond dissociation enthalpy.