Acids based on carborane anions as conjugate bases (Figure 1) are a new class of Brønsted (protic) acids, notable for their "strong yet gentle" qualities.[1] For example, whereas conventional strong acids (e.g. H 2 SO 4 ) and superacids (e.g. HFSO 3 /SbF 5 ) decompose fullerenes even at low temperatures, the carborane acid H(CHB 11 H 5 Cl 6 ) cleanly protonates C 60 at room temperature to give the isolable salt [HC 60 ] [CHB 11 H 5 Cl 6 ]. We now show that carborane acids are the

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Large, inert, weakly basic carborane anions of the icosahedral type CHB11R5X6 - (R = H, Me; X = Cl, Br) allow ready isolation and structural characterization of discrete salts of the solvated proton, [H(solvent) x ][CHB11R5X6], (solvent = common O-atom donor). These oxonium ion Brønsted acids are convenient reagents for the tuned delivery of protons to organic solvents with a specified number of donor solvent molecules and with acidities leveled to those of the chosen donor solvent. They have greater thermal stability than the popular [H(OEt2)2][BArF] acids based on fluorinated tetraphenylborate counterions because carborane anions can sustain much higher levels of acidity. When organic O-atom donors such as diethyl ether, tetrahydrofuran, benzophenone, and nitrobenzene are involved, the coordination number of the proton (x) in [H(solvent) x ]+ is two. A mixed species involving the [H(H2O)(diethyl ether)]+ ion has also been isolated. These solid-state structures provide expectations for the predominant molecular structures of solvated protons in solution and take into account that water is an inevitable impurity in organic solvents. The O···O distances are all short, lying within the range from 2.35 to 2.48 Å. They are consistent with strong, linear O···H···O hydrogen bonding. Density functional theory calculations indicate that all H(solvent)2 + cations have low barriers to movement of the proton within an interval along the O···H···O trajectory, i.e., they are examples of so-called SSLB H-bonds (short, strong, low-barrier). Unusually broadened IR bands, diagnostic of SSLB H-bonds, are observed in these H(solvent)2 + cations.