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

• Published in: European Journal of Inorganic Chemistry Vol. 2011; no. 20; pp. 3076 - 3081
• Main Authors: Soltner, Theresa, Goetz, Nadine R., Kornath, Andreas
• Format: Book Review
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.07.2011; WILEY‐VCH Verlag
• Subjects: Protonation; Structure elucidation; Sulfonium salts; Superacidic systems
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201001339

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. Trifluoromethanesulfonic anhydride reacts with superacidic solutions HF/SbF5 to form its corresponding salt CF3SO3H2+SbF6–, which is the protonated form of trifluoromethanesulfonic acid. The salt has been characterized by vibrational spectroscopy and single‐crystal structural analysis. The experimental data were also compared to quantum chemical calculations for the CF3SO3H2(HF)2+ cation.