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Theoretical insights into photo-induced isomerization mechanisms of phenylsulfinyl radical PhSO˙.

Sulfinyl radicals (R-SO˙) play important roles in lots of reactions, while the isomer oxathiyl radicals (R-OS˙) and the isomerization between them are rarely observed due to the poor stability of R-OS˙. In this work, the complete active space self-consistent field (CASSCF) and its multi-state second order perturbation (MS-CASPT2) methods were employed to study the photo-induced reaction mechanisms of phenylsulfinyl radical PhSO˙ 1 and its isomer phenoxathiyl radical PhOS˙ 2. Our results show that 1 and 2 have similar singly occupied molecular orbitals in the ground state but different properties in the excited state, which determine their diverse behaviors after irradiation. Radical 1 can generate 2 by light irradiation, but 2 produces isomerization product 3 (2-hydroxyphenylthiyl radical) and ring-opening product 4 (acyclic thioketoketene radical) in two paths via S atom migration intermediate Int1 (2-carbonylcyclohexadienthiyl radical). The former path involves consequent hydrogen shift reactions with a strongly exothermic process while the latter path involves both ring-expansion and ring-opening processes with a high barrier, resulting in a structural and energetic preference for the former path. Moreover, we revealed several conical intersections that participate in the reactions and facilitate the photochemical processes. Our calculations not only remain consistent with and clarify the experimental observations (X. Zeng, et al., J. Am. Chem. Soc., 2018, 140(31), 9972-9978) but also enrich the knowledge of sulfinyl radicals and isomer oxathiyl radicals.