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The thermally unstable, primary perfluoroalcohols, CF3OH, C2F5OH, and nC3F7OH, were conveniently prepared from the corresponding carbonyl compounds in anhydrous HF solution. Experimental values for the reaction enthalpies and entropies were derived from the temperature dependence of the RfCOF+HF⇄RfCF2OH (Rf=F, CF3, CF3CF2) equilibria by NMR spectroscopy. Electronic structure calculations of the gas‐phase and solution reaction energies, gas‐phase acidities and heats of formation were carried out at the G3MP2 level, showing that these compounds are strong acids. Protonation of these alcohols in HF/SbF5 produced the perfluoroalkyl oxonium salts RfCF2OH2+SbF6−. Highly acidic alcohols: The thermally unstable primary perfluorinated alcohols, CF3OH, C2F5OH, and nC3F7OH, and their oxonium salts were prepared from the corresponding carbonyl compounds in anhydrous HF and superacidic HF/SbF5 solutions. NMR spectroscopy allowed for the determination of experimental energy values obtained from the temperature dependence of the equilibria. Theoretical calculation of energetics, gas‐phase acidities and heats of formation at the G3MP2 level showed the strong acidic nature of these alcohols. [ABSTRACT FROM AUTHOR]

Perfluoroalcohols: Although thermally unstable, these alcohols can be readily accessed through equilibria of the corresponding acyl fluorides with HF in anhydrous HF solution. These equilibria can be shifted to the side of the alcohols by trapping them as oxonium salts, ethers or alkoxides, thus making these reactions synthetically useful. More information can be found in the Communication by K. O. Christe et al. on page 16742. [ABSTRACT FROM AUTHOR]