IR spectroscopic study of allylperoxy radical and products of its phototransformations in the Ar matrix

Article abstract of DOI:10.1007/BF01433741

Matrix IR spectra of an allylperoxy radical (1) obtained by co-condensation of allyl radicals and molecular oxygen into an argon matrix at 12 K have been studied. The bands observed in the matrix IR spectrum are assigned to normal vibrations on the basis of ab initio calculations of radical 1 and its isotope-substituted analog C₃H₅¹⁸O₂ (1a). The band at 1128.6 cm^-1 is assigned to the stretching vibration of the O-O bond. The products of photodecomposition of radical 1 under UV irradiation (λ > 248 nm) have been studied. A vinylacyl radical (2) with a characteristic high vibrational v(C=O) frequency of 1823.1 cm^-1 has been observed among the products of photolysis of 1. According to the data of quantum chemical calculations, some delocalization of a free electron between an oxygen atom and two C atoms is observed in radical 2.