Theoretical and experimental study of a new thiosulfonate derivative: methyl trifluoromethanethiosulfonate, CF3SO2SCH3. Conformational transferability in CX3SO2S-R compounds

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

INORGANICA CHIMICA ACTA

ELSEVIER SCIENCE SA

Lugar: Amsterdam; Año: 2017 vol. 455 p. 254 - 261

0020-1693

Methyl trifluoromethanethiosulfonate, CF3SO2SCH3, was synthesized and characterized by 13CNMR,19F-, NMR, and vibrational spectroscopy. This structural study was supported by MP2and DFT (B3LYP and MPW1PW91) calculations, which revealed a strong dependence of thetheoretical structure on the polarization of the basis set. Theoretical data indicate that only oneconformer, gauche, is predicted by rotating around the S?S bond. This conformationalpreference was studied using the total energy scheme and natural bond orbital partition scheme.These results evidence that electron delocalization and especially LP S s* C(1)-S interactionsplay an interesting role in the reactivity-structure connection of oxoesters and thioesters.Gas and liquid infrared and liquid Raman spectra were recorded and assigned. The experimentalvibrational data along with theoretical force constants (B3LYP) were used to define a scaledquantum mechanical force field, which enabled the reproduction of the measured frequencieswith a final root-mean-square deviation of 8.06 cm?1.