Substituent Effects on the N-H Bond Dissociation Enthalpies, Ionization Energies, Acidities, and Radical Scavenging Behavior of 3,7-Disubstituted Phenoxazines and 3,7-Disubstituted Phenothiazines.

The substituent effects on the N-H bond dissociation enthalpies (BDE), ionization energies (IE), acidities (proton affinity, PA), and radical scavenging behavior of 3,7-disubstituted phenoxazines (PhozNHs) and 3,7-disubstituted phenothiazines (PhtzNHs) were determined using density functional theory, with the M05-2X functional in conjunction with the 6-311++G(d,p) basis set. These thermochemical parameters calculated in both gas phase and benzene solution with respect to the changes in several different substituents including halogen, electron-withdrawing, and electron-donating groups at both 3 and 7 positions in both PhozNHs and PhtzNHs systems were analyzed in terms of the inherent relationships between them with some quantitative substituent effect parameters. The kinetic rate constants of hydrogen-atom exchange reactions between PhozNH and PhtzNH derivatives with the HOO(•) radical were also calculated, and the effects of the substituents on the kinetic behaviors of these reactions were thereby quantitatively evaluated.