"Synthesis, Characterization and Gas Phase Conformational Properties of Chlorodifluoroacetylsulfenyl Chloride, CF2ClC(O)SCl

LUCAS RODRIGUEZ PIRANI; ERBEN, MAURICIO F.; HEGEL WILLNER; CARLOS O. DELLA VÉDOVA

JOURNAL OF MOLECULAR STRUCTURE

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2022 vol. 1267 p. 1 - 8

0022-2860

The simple chlorodifluoroacetylsulfenyl choride species, CF2ClC(O)SCl, has been synthetized for the first time by the reaction between chlorodifluorothioacetic acid, CF2ClC(O)SH, and elemental chlorine. This carbonyl sulfenyl derivative has been exhaustively characterized by multinuclear (19F, and 13C) NMR, FTIR, and FT-Raman spectroscopies. The compound melts at -95(2) °C and is a stable liquid at room temperature with an extrapolated boiling point of 96(1) ºC. Conformational properties were investigated using gas-phase infrared and liquid Raman spectroscopy techniques, in combination with quantum chemical calculations at the B3LYP/6-311+G(3df) level of approximation. The coexistence of two conformations is confirmed in the gas phase, characterized by two orientations (gauche and syn) of the C-Cl single bond of the ?CF2Cl group with respect to the C=O double bond. The synperiplanar (syn) conformation in the sulfenyl carbonyl chloride moiety is characterized by the C=O double bond and the S-Cl single bond adopting a mutual synperiplanar orientation. The lowest energy conformation is the gauche-syn, with the second anti-syn form higher in energy by around 1.0 kcal/mol