Gas-phase acidities of some neutral Bronsted superacids: A DFT and ab initio study

For the first time G2 or G2(MP2) calculations or both have been performed t o calculate the acidity and deprotonation enthalpy of classical strong mine ral acids HClO4, CF3SO3H, FSO3H, H2SO4, HBF4, HPO3, and HNO3. Also, the int rinsic acidities and gas-phase deprotonation enthalpies for 39 neutral stro ng or superstrong Bronsted acids, Bronsted-Lewis conjugate acids, and some compounds modeling the acidic clusters of zeolites were calculated using th e DFT B3LYP 6-311+G** approach. DFT B3LYP method at 6-31+G* basis was used for the calculation of the intrinsic Bronsted acidities of the conjugate ac ids of the carborane anion CB11H12- and its mono-. hexa-, and dodecafluorin ated analogues. G2 and G2(MP2) theories describe the acidities of different compounds better than DFT B3LYP//6-311+G**. However, the DFT results could also be used for the estimation of the acidity of compounds which are out of reach of G2 or G2(MP2) theory. The estimated Delta G(acid) values obtain ed this way can be used as the substitutes for the unavailable experimental values, especially for those (rather numerous) compounds for which the exp erimental determination of Delta G(acid) is very difficult. In the case of practically all considered families of compounds extremely high acidities ( low Delta G(acid) values) could be reached. if the compounds were started f rom KF as the parent acid, then the estimated Delta G(acid) as low as 249.0 kcal/mol (for F(OSO2)(4)H) could be reached by formation of Bronsted-Lewis conjugate acids by consecutive complexation with SO3 molecules. Also very low Delta G(acid) value (Delta G(acid)(HSbF6) = 255.5) could be reached by complexation of HF with SbF5. At least as high intrinsic acidities as in ca se of the strongest Bronsted-Lewis superacids could be reached in the case of progressive introduction of highly electronegative, correctly oriented p olarizable dipolar electron-accepting substituents into the acidity site. I ndeed, the introduction of five CN groups into cyclopentadiene is expected to lead to the acidity Delta G(acid) = 250.1 kcal/mol which is lower than t he corresponding quantity even for hexafluoroantimonic acid (Delta G(acid) = 255.5 kcal/mol). However, by far the strongest intrinsic Bronsted acidity (Delta G(acid) = 209 kcal/mol) for dodecafluorosubstituted carborane acid CB11F12H is predicted to exceed the intrinsic acidity of sulfuric acid by a bout 90 kcal/mol or by almost 70 powers of ten, whereas semi-empirical PM3 calculations suggest that the conjugate acid of the dodecatrifluoromethylmo nocarborane anion CB11(CF3)(12) could be the first neutral Bronsted superac id whose acidity (deprotonation energy) is expected to be below the landmar k 200 kcal/mol level. An approximate linear relationship is found to hold b etween the calculated gas-phase acidities of strong and superstrong Bronste d acids and the corresponding Hammett acidity functions of the correspondin g neat acids. The simultaneous existence of the widely overlapping areas on the gas-phase acidity scale of neutral and cationic Bronstrd acids evidenc es strongly for the feasibility of the spontaneous proton-transfer equilibr ia between neutral Bronsted acids and bases.