Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF 3 SO 2 SCH 3 . Conformational transferability in CX 3 SO 2 S-R compounds

DEFONSI LESTARD, M.E.; BEN ALTABEF, A.; GALVÁN, J.E.; TUTTOLOMONDO, M.E.; CONTRERAS AGUILAR, E.; ULIC, S.E.

INORGANICA CHIMICA ACTA

ELSEVIER SCIENCE SA

Año: 2017 vol. 455 p. 254 - 261

0020-1693

Methyl trifluoromethanethiosulfonate, CF3SO2SCH3, was synthesized and characterized by 13C NMR, 19FNMR, and vibrational spectroscopy. This structural study was supported by MP2 and DFT (B3LYP andMPW1PW91) calculations, which revealed a strong dependence of the theoretical structure on the polarizationof the basis set. Theoretical data indicate that only one conformer, gauche, is predicted by rotatingaround the S?S bond. This conformational preference was studied using the total energy scheme and naturalbond orbital partition scheme. These results evidence that electron delocalization and especially LPS?r⁄ C(1)-S interactions play an interesting role in the reactivity-structure connection of oxoesters andthioesters.Gas and liquid infrared and liquid Raman spectra were recorded and assigned. The experimental vibrationaldata along with theoretical force constants (B3LYP) were used to define a scaled quantum mechanicalforce field, which enabled the reproduction of the measured frequencies with a final root-meansquaredeviation of 8.06 cm1.