Isolating benzenium ion salts.

When partnered with carborane anions, arenium ions are remarkably stable. Previously investigated only at subambient temperatures in highly superacidic media, protonated benzene is readily isolated as a crystalline salt, thermally stable to >150 degrees C. Salts of the type [H(arene)][carborane] have been prepared by protonating benzene, toluene, m-xylene, mesitylene, and hexamethylbenzene with the carborane superacid H(CB(11)HR(5)X(6)) (R = H, Me; X = Cl, Br). They have been characterized by elemental analysis, X-ray crystallography, NMR and IR methods. Solid-state (13)C NMR spectra are similar to those observed earlier in solution, indicating that lattice interactions are comparable to solution solvation effects. The acidic proton(s) of the arenium cations interact weakly with the halide substituents of the anion via ion pairing. This is reflected in the dependence of the C-H stretching frequency on the basicity of the carborane anion. Bond lengths in the arenium ions are consistent with predominant cyclohexadienyl cation character, but charge distribution within the cation is less well represented by this resonance form. Structural and vibrational comparison to theory is made for the benzenium ion (C(6)H(7)(+)) with density functional theory at B3LYP/6-31G and B3P86/6-311+G(d,p) levels. The stability of these salts elevates arenium ions from the status of transients (Wheland intermediates) to reagents. They have been used to bracket the solution-phase basicity of C(60) between that of mesitylene and xylene.