Formation of thioketenes by thermal fragmentation of 1,2-dithiol-3-ones

Abstract
Thioketenes 6 are formed in a Wolff-type rearrangement together with OCS by flash vacuum thermolysis (FVT) of 1,2-dithiol-3-ones 4 and identified by a combination of Ar matrix isolation FTIR sepctroscopy and collisional activation mass spectrometry (CAMS). The thioketenes all have strong IR absorptions in the 1750 cm-1 region ascribed to the CCS stretching vibration. The matrix IR and the CAMS of thioketenes 6a, 6d and 6e are identical with those of authentic samples generated by FVT of 1,2,3-thiadiazoles 7a, 7d and 2,3-dihydrobenzothiophene-2,3-dione 9, respectively. A competing fragmentation of the dithiolones leads to the corresponding acetylenes. CO and S2 were also identified.

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