Myths about the proton. The nature of H+ in condensed media.

Recent research has taught us that most protonated species are decidedly not well represented by a simple proton addition. What is the actual nature of the hydrogen ion (the "proton") when H(+), HA, H2A(+), and so forth are written in formulas, chemical equations, and acid catalyzed reactions? In condensed media, H(+) must be solvated and is nearly always dicoordinate, as illustrated by isolable bisdiethyletherate salts having H(OEt2)2(+) cations and weakly coordinating anions. Even carbocations such as protonated alkenes have significant C-H···anion hydrogen bonding that gives the active protons two-coordinate character. Hydrogen bonding is everywhere, particularly when acids are involved. In contrast to the normal, asymmetric O-H···O hydrogen bonding found in water, ice, and proteins, short, strong, low-barrier (SSLB) H-bonding commonly appears when strong acids are present. Unusually low frequency IR νOHO bands are a good indicator of SSLB H-bonds, and curiously, bands associated with group vibrations near H(+) in low-barrier H-bonding often disappear from the IR spectrum. Writing H3O(+) (the Eigen ion), as often appears in textbooks, might seem more realistic than H(+) for an ionized acid in water. However, this, too, is an unrealistic description of H(aq)(+). The dihydrated H(+) in the H5O2(+) cation (the Zundel ion) gets somewhat closer but still fails to rationalize all the experimental and computational data on H(aq)(+). Researchers do not understand the broad swath of IR absorption from H(aq)(+), known as the "continuous broad absorption" (cba). Theory has not reproduced the cba, but it appears to be the signature of delocalized protons whose motion is faster than the IR time scale. What does this mean for reaction mechanisms involving H(aq)(+)? For the past decade, the carborane acid H(CHB11Cl11) has been the strongest known Brønsted acid. (It is now surpassed by the fluorinated analogue H(CHB11F11).) Carborane acids are strong enough to protonate alkanes at room temperature, giving H2 and carbocations. They protonate chloroalkanes to give dialkylchloronium ions, which decay to carbocations. By partially protonating an oxonium cation, they get as close to the fabled H4O(2+) ion as can be achieved outside of a computer.