PHOTOLYSIS OF ALLENE-OZONE MIXTURES AT 647 nm IN CRYOGENIC MATRICES. Part 1. Formation of allene oxide

Article abstract of DOI:10.1016/0022-2860(89)80083-3

Matrix studies of the photolytic reaction at 647 nm between allene and ozone were carried out at 12 K.Primary photoproducts include carbon monoxide, acrolein (cis and trans), cyclopropanone, ketene, ethylene, allene oxide, and formaldehyde.In Ar and Kr matrices both acrolein and cyclopropanone are produced in high yields, whereas in Xe matrices cyclopropanone is the major product.Infrared spectra for cyclopropanone and ith oxygen-18 and deuterium substitutes are reported.The carbonyl stretch for cyclopropanone is observed at 1815 cm^-1 in an Ar matrix.Also reported is the first synthesis of allene oxide.The carbon-carbon double bond stretch is observed at 1823.4 cm^-1 and it exhibits a small oxygen-18 shift.The change in product distribution is discussed in terms of heavy atom spin-orbit enhancement of singlet-triplet excitation, so that in xenon reaction takes place on a triplet surface, whereas in argon it occurs on a singlet surface.