A ¹⁹F nuclear magnetic resonance investigation of the formation of Sb₂F₁₁⁻ and Sb_nF_5n+1⁻ in the CsF–SbF₅, t-butyl halide–SbF₅, and tetraalkylammonium hexafluoroantimonate–SbF₅ systems

Abstract

Fluorine nuclear magnetic resonance spectra have been obtained for the t-butyl fluoride–SbF5, t-butyl chloride–SbF5, tetraethylammonium hexafluoroantimonate–SbF5, and cesium fluoride–SbF5 systems, both with and without SO2 solvent. In SO2 solution the anion is Sb2F11− for all the systems, any remaining SbF5 being converted to SbF5•SO2. It is concluded that in the systems that do not contain SO2, higher polymeric anions SbnF5n+1−, where n > 2, are present. t-Butyl chloride and t-butyl fluoride give the t-butyl carbonium ion, as has been previously reported. Tetrabutylammonium and benzyltri-methylammonium cations appear to decompose to a carbonium ion and an adduct SbF5•NR3 in the presence of SbF5.

Ternary charge-transfer complexes. III. Complexes with Group V elements in the anion

“…hexamethylbenzene are listed in Table 2. SbF5 co-ordinates strongly with the SOz solvent to give axial and equatorial fluorine ligands (28). The chemical shifts and observable fluorine spin coupling in this system are strongly temperature-and concentration-dependant, the present results being for concentrated room temperature solutions.…”

A 19F Nuclear Magnetic Resonance Study of Halogen Exchange between Antimony Pentafluoride and Inorganic Chlorides. Complexes of Antimony and Arsenic Pentafluorides with Carbonyl Fluoride

“…The basic methods of sample preparation have been described in earlier papers (3)(4)(5). For SbF5/SbC15/ S02C1F, SbF5/S02C12/S02CIF, and SbF5/COF2/S02-ClF, the antimony compounds were added from all glass syringes to suitably adapted n.m.r.…”

The 19F nuclear magnetic resonance spectra of antimony pentafluoride, cis-Sb3F16− and higher polyanions SbnF5n+1−

“…In a previous paper (1) it was shown that when t-butyl fluoride is allowed to react with SbF, and the product is dissolved in SO, the solution contains the trimethylcarbonium ion, the Sb,F,,-anion, and the adduct SbF,. SO,.…”