Inhaltspezifische Aktionen

Capture and reactivity of an elusive carbon-sulfur centered biradical

Dennis Gerbig, Bastian Bernhardt, Raffael C. Wende and Peter R. Schreiner
J. Phys. Chem. 2020, 124, 2014–2018. DOI: 10.1021/acs.jpca.9b11795

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.