IR spectroscopic study of the dichloromethyl peroxyl radical and its deuterated analogs in the argon matrix

The dichloromethyl peroxyl radical (CHCl 2 OO • ) and its deuterated analog formed in the reaction of the corresponding dichloromethyl radicals with O 2 were studied by matrix IR spectroscopy. Dichloromethyl radicals are generated by the pyrolysis of the corresponding dichloromethyl iodides. The previously known spectral data are supplemented by an information about the peroxyl fragment vibrations, and the unidentified band at 1100.2 cm −1 is reliably assigned to the stretching vibration of the O-O bond. Its shift to 1040.6 cm −1 in the spectrum of the isotope-substituted radical CHCl 2 18 O 18 O • is observed. The IR spectrum of the deuterosubstituted radical CDCl 2 OO • was obtained for the first time. The processes of photolysis of the studied radicals proceeding with the formation of phosgene and formyl chloride are studied.