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Capture and Reactivity of an Elusive Carbon–Sulfur Centered Biradical

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journal contribution
posted on 02.03.2020 by Dennis Gerbig, Bastian Bernhardt, Raffael C. Wende, Peter R. Schreiner
The initial oxidation product of dimethyl sulfide in the marine boundary layer, the methyl thiomethyl radical, has remained elusive. A structurally analogous biradical with one radical center in the 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.