Using a combination of tandem mass spectrometry methodologies, collisional activation of fast (8 keV) or slow (20–30 eV) ion beams, neutralization–reionization and ion–molecule reactions, it is shown that thiosulfoxides X 2SS (X = H, CH 3, C 2H 5) are stable in the gas phase as radical cations as well as neutral molecules. The absence of isomerization into the more conventional disulfane structure, XSSX, is firmly demonstrated by ion-molecule reactions of the isomeric ions with methyl isocyanide and by collisional activation of “survivor” ions generated in neutralization–reionization experiments. All the mass spectral data have been recorded with a single hybrid mass spectrometer of sectors-quadrupole-sectors configuration. Molecular orbital calculations demonstrate that ionized thiosulfoxides and disulfanes are local minima on the MP2/6-31G∗ potential energy surface. The disulfane structures are found to be the most stable species by 91, 65 and 59 kJ/mol for X = H, CH 3 and C 2H 5, respectively. Heat of formation values of 1000, 810 and 760 kJ/mol are estimated for X 2SS ·+ ions (X = H, CH 3 and C 2H 5, respectively).
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