Reversible Generation of Labile Secondary Carbocations from Alcohols in the Nanospace of H-Mordenite and Their Long-Lasting Preservation at Ambient Temperature.

Secondary carbocations are rarely observed spectrometrically for prolonged durations at ambient temperatures because of their instability. In this study, when 4,4'-difluorobenzhydrol (1) was mixed with H-mordenite (H-Mor), the 4,4'-difluorodiphenylmethyl cation (2) was generated as the main product, identified by UV-vis and 13C-MAS NMR spectroscopies, and was preserved for over 1 week at ambient temperature. Surprisingly, the polymerization and disproportionation of 1 barely proceeded within the micropores of H-Mor. However, these side reactions prevailed in TfOH and formation of 2 was not observed. Preservation of other secondary carbocations from benzhydrol, 4,4'-dichlorobenzhydrol, and 9-fluorenol was also realized in H-Mor. It was confirmed that the generation of 2 from 1 was controlled by thermodynamic equilibrium rather than kinetic regulations. The equilibrium between 2 and 1 was accompanied by reversible chromism, which could be easily controlled by altering the moisture content in H-Mor. Moreover, novel insights into specific acid catalysis in zeolites densely populated with acid sites on the inner surface of micropores are described herein.