Matrix reactions of chlorine atoms with NO2 molecules

Abstract

Matrix reactions of chlorine atoms with NO₂ molecules diluted in argon yielded Cl–N bonded nitryl chloride ClNO₂ as well as the Cl–O bonded isomer nitrosyl hypochlorite ClONO. Infrared absorptions at 1714.1, 855.6, 398.0, and 390.4 cm⁻¹ were assigned to the ClONO species, which was shown from nitrogen‐15 and oxygen‐18 isotopic studies to be comprised of two weakly coupled diatomic radicals ClO and NO. Infrared spectroscopic evidence also suggested the presence of a third isomer OClNO which is produced by the insertion of a chlorine atom into an N–O bond of NO₂ as well as by the direct maxtrix combination of ClO and NO radicals. The photolytic behavior of the ClONO species indicates that it undergoes intramolecular rearrangement, in the argon matrix cage, to produce the more stable ClNO₂ form via a two‐step process which involves the OClNO molecule as an intermediate.