Hydrogen/Deuterium-Exchange Reactions of Methane with Aromatics and Cyclohexane Catalyzed by a Nanoscopic Aluminum Chlorofluoride

H/D-exchange reactions between methane and deuterated solvents such as [D-6]benzene and [D-12]cyclohexane were heterogeneously catalyzed by nanoscopic aluminum chlorofluoride (ACF=AlClxF3-x, x approximate to 0.05-0.3) under very mild conditions. (CNMR)-C-13 spectroscopy experiments at labeled methane revealed the formation of all isotopologues. AlCl3, AlBr3, HS-AlF3, -Al2O3, and -Al2O3 preheated at 700 degrees C did not show any H/D-exchange reaction of methane or [D-6]benzene. Mechanistically, electrophilic activation of methane was suggested at the ACF surface.