Radical and Concerted Mechanisms in Oxidations of Amines, Sulfides, and Alkenes by Peroxynitrite, Peroxynitrous Acid, and the Peroxynitrite−CO2 Adduct: Density Functional Theory Transition Structures and Energetics

The mechanisms of oxidations of amines, sulfides, and alkenes by peroxynitrous acid, as well as the mechanism for the conversion of peroxynitrous acid to nitric acid, have been investigated with density functional theory methods using the Becke3LYP functional and the 6-31G* basis set. Theoretical evidence is obtained for the mechanisms and transition states of oxidations by peroxynitrous acid both…