Infrared Matrix Isolation Studies of the Reactions of Dichloro- and Dibromomethane with Atomic Oxygen

Article abstract of DOI:10.1021/j100147a010

The reactions of atomic oxygen with CH2Cl2 and CH2Br2 trapped in argon matrices have been studied by FTIR spectroscopy.O(1D) and O(3P) were generated in situ by UV photolysis of co-deposited ozone.Products were identified by employing 18O and scrambled 18O/16O ozone as well as deuterated methylene halides.Kinetic studies performed on both CH2Cl2 and CH2Br2 with O(1D) under the same experimental conditions allowed the reaction pathway to be determined.With CH2Br2 as parent molecule, three routes were evident leading to (i) CHOBr,(ii) CO...(HBr)2, and (iii) CH2O.With CH2Cl2 as parent molecule, only the first two channels were observed.Carbonyl compounds rapidly decomposed under irradiation, and CO...(HX)2 was also produced as a secondary species.