The Protonation of CF₃SO₃H: Preparation and Characterization of Trifluoromethyldihydroxyoxosulfonium Hexafluoridoantimonate, CF₃SO₃H₂⁺SbF₆^–

Abstract

Trifluoromethanesulfonic anhydride reacts with superacidic solutions AF/SbF5 (A = H, D) to form their corresponding salts CF3SO3A2+SbF6–, which are protonated forms of trifluoromethanesulfonic acid and CF3SO2F as by‐product. The salts have been characterized by vibrational spectroscopy and single‐crystal structural analysis. CF3SO3H2+SbF6– crystallizes in the triclinic space group P$\bar {1}$ with two formula units in the unit cell: a = 709.29(5) pm, b = 763.46(5) pm, c = 882.15(6) pm; α = 71.884(6)°, β = 72.488(6)°, γ = 84.509(6)°; V = 432.97(5) Å3. The cations are linked with two strong hydrogen bonds to SbF6– anions to form chains. The experimental data were also compared to quantum chemical calculations for the CF3SO3H2(HF)2+ cation.

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