The Chemistry of Nitroso Oxides

Abstract

Nitroso oxides (RNOO) are the isoelectronic analogs of carbonyl oxides (R2COO) and ozone (O3) and, as well as these species, possess a three-centered 4π-electron system, which determines their chemical properties and reactivity unusual for a family of peroxides. The review is focused on the chemistry of the parent nitroso oxide (HNOO) and its aromatic analogs (ArNOO). The structure, spectral properties, methods for generation, reactivity and mechanisms of various transformations of these species both in the gas and condensed media are discussed in detail. An aromatic substituent significantly stabilizes the π-system of nitroso oxide. The typical reactions of nitroso oxides are O-transfer to an appropriate substrate or [3+2]-cycloaddition to unsaturated bonds. Special attention was paid to the redox isomerization of arylnitroso oxides with ring cleavage that leads to the formation of diene nitrile oxides. Keywords: aromatic azides; mechanism of reactions; nitrenes; nitroso oxides; photooxidation; reactive intermediates