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An Organotin Vanadate with Sodalite Topology and Catalytic Versatility in Oxidative Transformations

The new coordination polymer formulated as [Et3SnVO3] (1) has been synthesized and shown by a combined single‐crystal and synchrotron powder X‐ray diffraction structural analysis, supported by solid‐state NMR, to possess a three‐dimensional network structure with the sodalite topology, formed by tetravanadate polyanions, [V4O12]4−, that are linked by Et3Sn+ spacers. The catalytic versatility of compound 1 for liquid phase organic reactions was demonstrated by applying it for the epoxidation of olefins, the oxidative dehydrogenation of alcohols, and the oxidation of benzyl alcohol to benzaldehyde and benzoic acid, using tert‐butyl hydroperoxide (TBHP) as oxidant. Compound 1 acts a solid reservoir for soluble, catalytically active species, which promote high selectivities to the epoxide and carbonyl (aldehyde/ketone/acid) products. The epoxidation activity compares favorably with those reported for other organotin molybdate, tungstate and vanadate coordination polymers, and is superior to that displayed by the starting materials used for its synthesis (Et3SnBr and NH4VO3) and the metavanadate NBu4VO3.