Reaction of Phenylchlorocarbene in Oxygen-Doped Matrices

Article abstract of DOI:10.1021/ja00267a022

Irradiation of phenylchlorodiazirine at 10 K matrix isolated in argon gives phenylchlorocarbene.The carbene was characterized by IR, UV, and trapping with HCl.Warming an argon matrix containing O2 and the carbene to 35 K caused reaction to give the corresponding carbonyl oxide.The yellow-green (λ_max 400nm) carbonyl oxide was characterized by IR, Uv, and 18O2 labeling.Photolysis of the carbonyl oxide with visible light gave the corresponding dioxirane, benzoyl chloride, and ozone.The dioxirane, which showed only absorption tailing into the visible, was characterized by IR, 18O2 labeling, and subsequent photochemistry.Irradiation of the dioxirane (λ>/=420 nm) gave mainly phenyl chloroformate and a small amount of chlorobenzene and CO2.Possible mechanism for the novel spin-forbidden O2 addition are discussed.