Isomerization and Fragmentation Reactions on the [C₂SH₄] Potential Energy Surface: The Metastable Thione S-Methylide...

Thione S-methylide, parent species of the thiocarbonyl ylide family, is a 1,3-dipolar species on the [C₂SH₄] potential energy surface, not so much studied as its isomers, thiirane, vinyl thiol, and thioacetaldehyde. The conrotatory ring-closure reaction toward thiirane was studied in the 90s, but no complete analysis of the potential energy surface is available. In this paper, we report a computational study of the reaction scheme linking all species. We employed several computational methods (density functional theory, CCSD(T) composite schemes, and CASSCF/CASPT2 multireference procedures) to find the best description of thione S-methylide, its isomers, and transition states. The barrier from thiirane to thione S-methylide amounts to 52.2 kcal mol^-1 (against 17.6 kcal mol^-1 for the direct one), explaining why thiocarbonyl ylides cannot be prepared from thiiranes. Conversion of thiirane to vinyl thiol implies a large barrier, supporting why the reaction has been observed only at high temperatures. Fragmentations of thiirane to S(³P) or S(¹D) and ethylene as well as decomposition to hydrogen sulfide plus acetylene were also explored. Triplet and singlet open-shell species were identified as intermediates in the fragmentations, with energies lower than the transition state between thiirane and vinyl thiol, explaining the preference of the latter at low temperatures.