Singlet-oxygen generation in the catalytic reaction of dioxiranes with nucleophilic anions

Abstract

Nucleophilic anions such as Cl⁻, I⁻, Br⁻, t-BuO⁻, O₂⁻ and OH⁻ efficiently catalyze the decomposition of dimethyldioxirane (DMD) and methyl(trifluoromethyl)dioxirane (TFD). Singlet oxygen (¹O₂) is formed in these catalytic reactions, as demonstrated by the characteristic infrared chemiluminescence (IR-CL) at 1268 nm. The yield of ¹O₂ generation, measured by the IR-CL method, lies in the range between 2 and 98%, which depends on the particular anion employed. For the bromide ion, the catalytic decomposition of the dioxirane is in competition with the oxidation of Br⁻ to elemental bromine.