On the reactivity of surface methoxy species in acidic zeolites

The in situ preparation and isolation of surface methoxy species on acidic zeolites are followed by further investigations of their reactivity in heterogeneously catalyzed reactions. For the first time, the following solid-state NMR evidence for the high reactivity of surface methoxy species has been obtained: (i) Surface methoxy species react readily with ammonia on acidic zeolites at room temperature, by which methylamines and methylammonium cations are formed. (ii) The transformation of surface methoxy species to other alkoxy species can be achieved by the reaction of surface methoxy species and corresponding alkyl halides on acidic zeolites. (iii) Surface methoxy species react readily with hydrochloride, giving methyl chloride as the sole product. (iv) The classic Koch carbonylation reaction and Ritter reaction in solution can be performed with surface methoxy species on acidic zeolites. (v) Carbon monoxide and carbon dioxide are produced by the oxidation of surface methoxy species in the presence of oxygen. The stability and reactivity of surface methoxy species are discussed in comparison with other surface alkoxy species (> C₁ species).