Artículos de revistas
Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF3SO2SCH3. Conformational transferability in CX3SO2S-R compounds
Fecha
2017-01Registro en:
Galván, Jorge Edgardo; Contreras Aguilar, Elizabeth; Defonsi Lestard, Maria Eliana; Tuttolomondo, María Eugenia; Ulic, Sonia Elizabeth; et al.; Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF3SO2SCH3. Conformational transferability in CX3SO2S-R compounds; Elsevier Science Sa; Inorganica Chimica Acta; 455; Parte 1; 1-2017; 254-261
0020-1693
CONICET Digital
CONICET
Autor
Galván, Jorge Edgardo
Contreras Aguilar, Elizabeth
Defonsi Lestard, Maria Eliana
Tuttolomondo, María Eugenia
Ulic, Sonia Elizabeth
Ben Altabef, Aída
Resumen
Methyl trifluoromethanethiosulfonate, CF3SO2SCH3, was synthesized and characterized by 13C NMR, 19F NMR, and vibrational spectroscopy. This structural study was supported by MP2 and DFT (B3LYP and MPW1PW91) calculations, which revealed a strong dependence of the theoretical structure on the polarization of the basis set. Theoretical data indicate that only one conformer, gauche, is predicted by rotating around the S–S bond. This conformational preference was studied using the total energy scheme and natural bond orbital partition scheme. These results evidence that electron delocalization and especially LP S → σ∗ C(1)-S interactions play 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 experimental vibrational data along with theoretical force constants (B3LYP) were used to define a scaled quantum mechanical force field, which enabled the reproduction of the measured frequencies with a final root-mean-square deviation of 8.06 cm−1.