<p>Reaction of toluene (T) with HO<sup>●</sup>
produces addition products and the benzyl radical (TR). TR can react with HO<sup>●</sup>
or O<sub>2</sub> to produce oxygenated species, for many of which there is no
experimental information. We present here theoretically determined heats of
formation (HFs) of 17 such species using non-isodesmic reactions of TR+O<sub>2</sub>
and T+HO<sup>●</sup>+O<sub>2</sub>. For experimentally known HFs, we obtained a
reasonable correlation between experimental and theoretical data for G4
(r2=0.999) and M06/cc-pVQZ (r2=0.997) results. Previously unknown HFs of other
radicals (benzyloxy, spiro [1,2-dioxetane benzyl], hydroxyphenyl, and
benzylperoxy) and closed shell species (salicylic alcohol, benzo[b]oxetane and
p-hydroxy cyclohexa-2,5-dienone) were calculated using these methods. The
species studied and the enthalpies of formation obtained were: salycilic
alcohol, -69.7 ± 3.4 kcal/mol; benzyloxy radical, 28.4 ± 3.4 kcal/mol;
hydroxyphenyl radical, 37.3 ± 3.4 kcal/mol; benzo[b]oxetane, 23.7 ± 3.4
kcal/mol; spiro [1,2-oxoetane phenyl] radical, 57.3 ± 3.4 kcal/mol; p-hydroxy cyclohexan-2,5-dienone,
-42.1 ± 3.4 kcal/mol; and benzylperoxy radical, 28.5 ± 3.2 kcal/mol.</p>