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

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journal contribution
posted on 2005-03-21, 00:00 authored by Min Fang, Jack Passmore, Andreas Decken
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.