The H/D exchange of arenes in acidic media by transition-metal and main-group-metal complexes and common inorganic salts was studied. The influence of Lewis acidity, anions, charge, and ligands was evaluated. The results indicate that the determination of H/D exchange activity in acidic media is not related to the formation of metal–carbon bonds (i.e., C–H activation). The combined experimental data (regioselectivity, activation energy, kinetics, isotope effects, solvent effects) and DFT calculations point toward a proton catalysis mechanism. Thus, highly Lewis acidic metal compounds, such as aluminum(III) triflate, were extraordinarily active for the H/D exchange reactions. Indeed, the degree of H/D exchange reactivity allows for a comparative measurement of Lewis acidities
