A kinetic and products study of the reaction of 2,2-dimethyl-5-methoxyindan-1-ol (1) radical cation, in acidic aqueous solution (pH=<4) has been carried out. 1 + undergoes C-H deprotonation as the exclusive reaction with k=4.6x10 4 s - 1 . The kinetic data have been compared with those obtained for the radical cations of 1-(4-methoxyphenyl)ethanol (2) and 1-(4-methoxyphenyl)-2,2-dimethyl-1-propanol (3), suggesting that the deprotonation rate increases when the C-H bond is forced into a conformation where it is almost aligned with the π-system. The conclusion that overlap between the scissile bond and the π-system is an important requisite for the occurrence of bond cleavage is also supported by the results of DFT calculations carried out for 1 + and 3 + .