Electrospray ionization of a methanolic solution of Michler's hydrol blue, bis(4-(NN-dimethylamino)phenyl)methyl tetrafluoroborate, 1(+)BF(4)(-), produces the formal methanol adduct [1(+)center dot CH3OH], which shows an unusual gas-phase chemistry. Tandem mass-spectrometry experiments and complementary theoretical studies indicate that this adduct corresponds to the methyl ether of Michler's hydrol protonated at one of the dimethylamino groups, cation 3(+). Collision-induced dissociation of mass-selected 3(+) leads to two sequential expulsions of open-shell species, resulting in a formal loss Of [C2H6O], whereas no expulsion of methanol is observed. In contrast, interaction of gaseous 31 with a single molecule of a suitable base triggers an exoergic loss of methanol via proton-shuttle catalysis within the collision complex. The occurrence of this exothermic proton transfer also prevents the application of the otherwise successful kinetic method for the determination of the gas-phase proton affinity of the methyl ether of Michler's hydrol.