Syntheses and Characterization of the MF₆^- (M = As, Sb) Salts of the Simple Trithietanylium PhCS₃⁺ Cation and the Identity of PhCS₃Cl

MF₆^- (M = As or Sb) salts of a simple derivative of the trithietanylium 1, were synthesized for the first time by the reaction of PhCS₃Cl and AgMF₆ in liquid SO₂. 1SbF₆ was characterized by IR, FT-Raman, and NMR spectroscopy, elemental analysis, and a preliminary X-ray crystal structure. 1AsF₆ was characterized by ¹H NMR and FT-Raman spectroscopy. The calculated (MPW1PW91/3-21G* or 6-31G*) geometries, ¹H and ¹³C chemical shifts (MPW1PW91/6-311G(2DF)//MPW1PW91/3-21G*), and vibrational frequencies and intensities (MPW1PW91/6-31G*) were in satisfactory agreement with the observed values. The calculated π type molecular orbitals of (MPW1PW91/6-311+G*) and 1 (MPW1PW91/3-21G*) imply that the 6π ring has some aromatic character. 1SbF₆ undergoes a metathesis reaction with NBu₄Cl in liquid SO₂ to give PhCS₃Cl, which was characterized by vibrational spectroscopy and mass spectrometry. The evidence indicates that PhCS₃Cl has the ionic formulation with significant cation−anion interactions in the solid state. (Ar = 1-naphthyl), 14SbF₆, was prepared from ArCS₃Cl and AgSbF₆, suggesting that the synthesis of MF₆^- (M = As or Sb) salts of is potentially general for aryl derivatives. The structure of 14SbF₆ was established by ¹H and ¹³C NMR, IR, and FT-Raman spectroscopy, and theoretical calculations gave values in agreement with the experimental data.