Capture and Reactivity of an Elusive Carbon-Sulfur Centered Biradical

The initial oxidation product of dimethyl sulfide in the marine boundary layer, the methylthio methyl radical, has remained elusive. A structurally analogous biradical with one radical center in α-position to a sulfur atom could now be obtained by UV-irradiation of p-nitrobenzaldehyde dithiane isolated in solid dinitrogen (N2) or Ar at cryogenic temperatures. A spin-forbidden reaction with triplet dioxygen (3O2) does not occur. The dithiane of o-nitrobenzaldehyde rather undergoes a series of rearrangements under the same conditions, resulting in overall photodeprotection.