Hydrocarbon Bond Dissociation Energies

The best available values for homolytic bond dissociation energies (BDEs) of various classes of neutral compounds are considered in this review. (BDEs in ionic species is a legitimate subject that is touched on briefly and could easily be included in a longer review. The same can be said for heterolytic BDEs, which are not reviewed as such, although some of the ionic thermochemical data discussed yield values for these processes.) The major emphasis is on hydrocarbons and their nitrogen, oxygen, sulfur, halogen, and silicon-containing derivations, but limited data for inorganic molecules are included. The focus is particularly on prototypical radicals whose heats of formation, formerly thought to be well in hand, have recently been called into serious question. The intent is to include all the major types of sigma bonds, if not all specific cases where known or estimatable heats of formation allow bond dissociation energies to be generated. This review attempts to acknowledge all the standard techniques for measuring BDEs in polyatomic molecules and to offer critical analysis of selected portions of the literature. This leaves values that the authors recommend as the most likely to be correct at the time of this writing. 246 references, 9 tables.