IR SPECTROSCOPIC STUDY OF ALLYLPEROXY RADICAL AND PRODUCTS OF ITS PHOTOTRANSFORMATIONS IN THE AR MATRIX

Matrix IR spectra of an allylperoxy radical (1) obtained by co-condens ation of allyl radicals and molecular oxygen into an argon matrix at 1 2 K have been studied. The bands observed in the matrix IR spectrum ar e assigned to normal vibrations on the basis of ab initio calculations of radical 1 and its isotope-substituted analog (C3H5O2)-O-18 (1a). T he band at 1128.6 cm(-1) is assigned to the stretching vibration of th e O-O bond. The products of photodecomposition of radical 1 under UV i rradiation (lambda > 248 nn) have been studied. A vinylacyl radical (2 ) with a characteristic high vibrational nu(C=O) frequency of 1823.1 c m(-1) has been observed among the products of photolysis of 1. Accordi ng to the data of quantum chemical calculations, some delocalization o f a free electron between an oxygen atom and two C atoms is observed i n radical 2.