A 19F nuclear magnetic resonance study of the conjugate Brønsted–Lewis superacid HSO3F–SbF5. Part II.

Author:

Kühn-Velten Jobst,Bodenbinder Matthias,Bröchler Raimund,Hägele Gerhard,Aubke Friedhelm

Abstract

Solutions of SbF5 in HSO3F with xSbF5 = 0.012 to 0.405 are studied by 500 MHz 1H NMR (299 K) and 471 MHz 19F NMR (213–250 K), using NMR tubes fitted with fluoropolymer lining. The initial process during dissolution is the fast solvolysis of monomeric SbF5 in HSO3F according to SbF5 + nHSO3F [Formula: see text] SbF5 – n(SO3F)n + nHF (n = 1, 2). All HF formed during solvolysis will no longer be removed by reaction with glass, but will remain in the superacid system. Besides participation in the fast formation of various fluoro-fluorosulfato anions [SbF6 – n(SO3F)n]– (n = 0, 1, 2) and acidium ions [H2X]+(solv.) (X= F, SO3F), HF is involved in slow-exchange reactions of the type [SbF6 – n(SO3F)n]–(solv.) + HF [Formula: see text] [SbF7 – n(SO3F)n– 1]–(solv.) + HSO3F (n = 1, 2) detected because of a delay of 3 months between sample preparation and measurements and confirmed by repeating theses measurements after a further 3 months. There are three notable differences to our earlier study, affecting concentrations of the fluoro-fluorosulfato antimonate anions observed: (i) in dilute solutions [SbF6]– is formed in high concentrations (34.7–76.1%), with [Sb2F11]– now clearly detected at intermediate to high SbF5 concentrations (up to 5.8%); (ii) bis-fluorosulfato anions (cis-, trans-[SbF4(SO3F)2]–) are found in much lower concentrations only, which decrease further with time, while tris-fluorosulfato anions ([SbF3(SO3F)3]–) are now no longer observed; (iii) these reduced concentrations of poly-fluorosulfato anions in dilute solutions are responsible for the formation of fewer µ-SO3F-oligomers at lower concentrations, when more SbF5 is added. As a consequence, the HSO3F–SbF5 magic acid system is now less complex than found previously and only seven anionic species are clearly observed. Key words: superacids, antimony(V) fluoroanions, 1H NMR, 19F NMR, solvolysis.

Publisher

Canadian Science Publishing

Subject

Organic Chemistry,General Chemistry,Catalysis

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