Alkane C−H Bond Activation in Zeolites:  Evidence for Direct Protium Exchange

The mechanism of alkane C-H bond activation in heterogeneous acid catalysis is unknown. (1)H solid-state NMR techniques have been used to simultaneously detect the reactivity of both catalyst and alkane reactant protons in a true in-situ experimental design. Specifically, the activation of isobutane C-H bonds by the solid acid zeolite HZSM-5 is directly observed, and the rate of proton transfer between the solid catalyst surface and gaseous isobutane is quantitatively measured using isotopic (1)H/(2)H exchange methods. An observable adsorption complex forms between the isobutane and the primary Bronsted acid site of ZSM-5, which leads to proton exchange between the zeolite surface and the isobutane methyl groups at temperatures (273 K) much lower than previously reported. The secondary acid site in ZSM-5 is less accessible to or less reactive with the isobutane molecule. Simultaneous detection of protium loss from the Bronsted acid site and protium gain by perdeuterated isobutane reveals a common rate constant equal to 4.1-4.6 x 10(-4) s(-1) at 298 K, but at lower temperatures, the transition between this and a much slower rate process is resolved. The measured activation energy for isobutane H/D exchange is 57 kJ/mol. In all experiments, the isobutane reagent was purified to eliminate any unsaturated impurities that might serve as initiators for carbenium-ion mechanisms, and the active catalyst was free of any organic contaminants that might serve as a source of unsaturated initiators. In total, our results are consistent with direct proton exchange between the zeolite surface and the methyl groups of isobutane.