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. 2024 Nov 15;26(45):9619-9624.
doi: 10.1021/acs.orglett.4c02849. Epub 2024 Sep 4.

Re-examination of the Claimed Isolation of Stable Noncyclic 1,2-Disulfoxides

Eric Block  1 , Julien J H Cotelesage  2 , Evgeny Dikarev  1 , Benedetta Garosi  1 , Graham N George  2 , Rabi A Musah  1 , Linda I Vogt  2 , Zheng Wei  1 , Yuxuan Zhang  1
Affiliations

Re-examination of the Claimed Isolation of Stable Noncyclic 1,2-Disulfoxides

Eric Block et al. Org Lett. .

Abstract

Re-examination of the claimed isolation and X-ray characterization of di-p-tolyl and dimesityl 1,2-disulfoxides from thermolysis of the corresponding aryl sulfinimines and thiosulfinates showed that the isolated disulfide dioxides are instead the well-known isomeric thiosulfonates, as confirmed by XAS, DART-MS, X-ray, IR and NMR methods. Concerns with the original X-ray structures are addressed. Our results agree with the DFT prediction of very weak diaryl 1,2-disulfoxide S-S bond dissociation enthalpies. For now, room-temperature-stable noncyclic 1,2-disulfoxides remain unknown.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Stable cyclic 1,2-disulfoxide trans-1.
Figure 2
Figure 2
Thermolysis of N-benzylidenearenesulfinimines 4. For Ar in 4–9, a = p-tolyl and b = mesityl.,
Figure 3
Figure 3
Sulfur K-edge XAS of the p-tolyl series 8a (disulfide), 6a (thiosulfinate), 7a (thiosulfonate). The black lines show experimental spectra, while the green lines show the DFT spectral simulations. Compounds 6a and 7a contain sulfur in two different formal oxidation states, and the predicted spectra of these different sulfurs are shown by the blue (reduced) and red (oxidized) lines along with stick spectra showing the DFT computed transition energies and intensities. The predicted spectrum of 1,2-disulfoxide 9a is shown for comparison and can be seen to be distinct from all of the experimental spectra. Similar results were found for the mesityl series 8b, 6b, and 7b (not shown).
Figure 4
Figure 4
Radical disproportionation pathways for diaryl thiosulfinates (a = p-tolyl, b = mesityl).
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References

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