Evidence of IR-Induced Chemistry in a Neat Solid: Tautomerization of Thiotropolone by Thermal, Electronic, and Vibrational Excitations
Nelson A. M. Pereira, Cláudio M. Nunes, Igor Reva, Rui Fausto
Abstract
Thiotropolone isolated in argon and xenon matrices (as monomers) or in a neat solid (as the crystalline or amorphous state) at low temperature was found to exist only in the thione-enol form. Visible light irradiation (λ ≥ 400 nm) leads to thione-enol → thiol-keto tautomerization in matrices and under neat solid conditions at 15 K. The assignment of the IR spectra of the two thiotropolone tautomers (thione-enol and thiol-keto) was carried out with the support of B3LYP/6-311+G(2d,p) computations. The thiol-keto form generated in situ in a neat solid was found to tautomerize back to the thione-enol upon annealing up to 100 K. Gaussian-4 (G4) computations estimate that such a tautomerization process has an energy barrier of ∼25 kJ mol–1, which is consistent with the observations. Moreover, it was found that narrowband IR irradiation of the thiol-keto form in a neat solid, at the frequency of its CH stretching overtones/combination modes, also induces tautomerization to the thione-enol form. Such a result constitutes an important demonstration of vibrationally induced chemistry under neat solid conditions.