Oxygen, bond dissociation energy

Physical Properties. Properties of some alkyl peroxyesters are Hsted in Table 13 and the properties of some alkyl areneperoxysulfonates are given in Table 14. Mass spectra (226), total energies, and dipole moments (227) oxygen—oxygen bond-dissociation energies (44,228) and boiling points, melting points, densities, and refractive indexes (44,168,213) have been reported for a variety of tert-huty peroxycarboxylates. 

Bond dissociation energies (BDEs) for the oxygen—oxygen and oxygen— hydrogen bonds are 167—184 kj/mol (40.0—44.0 kcal/mol) and 375 kj/mol (89.6 kcal/mol), respectively (10,45). Heats of formation, entropies, andheat capacities of hydroperoxides have been summarized (9). Hydroperoxides exist as hydrogen-bonded dimers in nonpolar solvents and readily form hydrogen-bonded associations with ethers, alcohols, amines, ketones, sulfoxides, and carboxyhc acids (46). Other physical properties of hydroperoxides have been reported (46). 

FIGURE 2.16 The bond dissociation energies, in kilojoules per mole of nitrogen, oxygen, and fluorine molecules. Note how the bonds weaken in the change from a triple bond in N, to a single bond in F,... 

Fig. 9 Deprotonation of cations radicals of synthetic analogs of NADH by oxygen or nitrogen bases in acetonitrile. Correlation between the intrinsic barrier and the homolytic bond dissociation energy of the cation radical (AH + —> A+ + H ).

The similarity of the structure of peroxynitrous acid to the simplest peroxy acid, per-oxyformic acid, immediately raised the question as to its relative reactivity as an oxygen atom donor. This became particularly relevant when it was recognized that the 0—0 bond dissociation energy (AG° = 21 kcalmoR ) of HO—ONO was much lower than that of more typical peroxides. Consequently, peroxynitrous acid (HO-ONO) can be both a one- and two-electron oxidant. Since the 0-0 bond in HO-ONO is so labile, its chemistry is also consistent in many cases with that of the free hydroxyl radical. 

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