The features of initiation of free radical reactions in polymers by dimers of nitrogen dioxide are considered. The conversion of planar dimers into nitrosyl nitrate in the presence of amide groups of macromolecules has been revealed. Nitrosyl nitrate initiates radical reactions in oxidative primary process of electron transfer with formation of intermediate radical cations and nitric oxide. As a result of subsequent reactions, nitrogen-containing radicals are produced. The dimer conversion has been exhibited by estimation of the oxyaminoxyl radical yield in characteristic reaction of P-benzoquinone with nitrogen dioxide on addition of aromatic polyamide and polyvinylpyrrolidone to reacting system. The isomerization of planar dimers is efficient in their complexes with amide groups, as confirmed by ab initio calculations. (C) 2007 Wiley Periodicals, Inc.