The DFT B3LYP/6-31G* calculations were carried out for the reactions of C6H6 and Ad(3) C6H3 (Ad = 1,3,5-adamantyl) with superelectrophile CBr3+ as a model of superelectrophilic catalyst CBr3+ Al2Br7-. The reaction of C6H6 with CBr3+ proceeds via the classical scheme of electrophilic reactions of aromatic C-H bond to form initially the barrier-free sigma-complex C6H6CBr3+. This mechanism was confirmed by the aug-cc-pVDZ basis set calculations. The reaction of Ad(3)C(6)H(3) with CBr3+ occurs via a quite novel mechanism involving aryl cation formation followed by hydride abstraction of the Ar+ from the 2-Ad group and the rearrangement of the 2-Ad(+) cation into the 4-phenyl-4-protoadamantyl cation. The hydride transfer from both arenes was shown to be more favorable than H radical transfer by more than 40 and 55 kcal mol(-1) in the case of C6H6 and Ad(3)C(6)H(3), respectively. (C) 2016 Elsevier B.V. All rights reserved.