Conformational properties of thiazyldifluoride imidosulfurdifluoride, NSF2NSF2, and thiazyldifluoride imidosulfuryldifluoride, NSF2NS(O)F2: Vibrational spectra and quantum chemical calculations

Abstract

Thiazyldifluoride imidosulfurdifluoride, Ntriple bondSF2single bondNdouble bondSF2, and thiazyldifluoride imidosulfuryldifluoride, Ntriple bondSF2single bondNdouble bondS(O)F2 were studied by vibrational spectroscopy (FT IR (gas) and Raman (liquid)) and by quantum chemical calculations (B3LYP and MP2 with 6-31G(d) and 6-311+G(2df) basis sets). Depending on the computational method two, three or four stable conformers are predicted for Ntriple bondSF2single bondNdouble bondSF2, whereas all methods predict the existence of four stable conformers for Ntriple bondSF2single bondNdouble bondS(O)F2. The most stable conformer of both compounds possesses cis–syn structure (cis configuration of the Ntriple bondSsingle bondNdouble bondS skeleton and syn orientation of the terminal SF2 and S(O)F2 groups relative to the Nsingle bondS single bond). The experimental vibrational spectra were assigned on the basis of reported data for analogous compounds and calculated wavenumbers for the most stable conformers. The NS triple, double and single bond lenghts are discussed and compared to such bonds in other compounds.