Conversion of methyl halides to hydrocarbons on basic zeolites: A discovery by in Situ NMR

Article abstract of DOI:10.1021/ja00064a037

It is shown that methyl halides (I, Br, Cl) react to form ethylene and other hydrocarbons on basic, alkali metal-exchanged zeolites at low temperatures. For example, methyl iodide is converted to ethylene on CsX zeolite at ca. 500 K. The order of reactivity of various catalyst/adsorbate combinations is consistent with the predictions of elementary chemical principles. The order of reactivity of the methyl halides follows the expected leaving-group trend. The activity of the catalyst framework correlates with its basicity (or nucleophilicity). All reactions were performed in a batch mode in sealed magic angle spinning (MAS) rotors while the contents were continuously monitored by in situ ¹³C NMR. Methyl iodide reacts on CsX below room temperature to form a framework-bound methoxy species in high yield. An analogous ethoxy species readily formed from ethyl iodide. These species were characterized in detail. The ethoxy species was quantitatively converted to ethylene below 500 K. ¹³³Cs MAS NMR was used to characterize the interactions of methyl iodide and other adsorbates with the cation in zeolite CsZSM-5. Solvation of the alkali metal cation was reflected in large, loading-dependent chemical shifts for ¹³³Cs. Interactions between the cation and adsorbates were also reflected in the ¹³C shifts of the alkyl halides and ethylene. The cumulative evidence suggests a mechanism for carbon-carbon bond formation analogous to one proposed by Chang and co-workers for methanol-to-gasoline chemistry on acidic zeolites (J. Chem. Soc., Chem. Commun. 1987, 1320) that involves framework-bound methoxy and ethoxy species. The mechanism for methyl halide conversion is proposed to include roles for the basicity of the zeolite framework as well as the Lewis acidity of the cation.