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Chemistry. 2013 Apr 15;19(16):5191-7. doi: 10.1002/chem.201204563. Epub 2013 Feb 27.

A soluble phosphorus-centered Keggin polyoxoniobate with bicapping vanadyl groups.

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  • 1Department of Chemistry, University of California, Davis, One Shields Ave., Davis, CA 95616, USA.


A water-soluble tetramethylammonium (TMA) salt of a novel Keggin-type polyoxoniobate has been isolated as TMA9[PV2Nb12O42]·19H2O (1). This species contains a central phosphorus site and two capping vanadyl sites. Previously only a single example of a phosphorus-containing polyoxoniobate, [(PO2)3PNb9O34](15-), was known, which is a lacunary Keggin ion decorated with three PO2 units. However, that cluster was isolated as an insoluble structure consisting of chains linked by sodium counterions. In contrast, the [PV2Nb12O42](9-) cluster in 1 is stable over a wide pH range, as evident by (31)P and (51)V NMR, UV/Vis spectroscopy, and ESI-MS spectrometry. The ease of substitution of phosphate into the central tetrahedral position suggests that other oxoanions can be similarly substituted, promising a richer set of structures in this class.

Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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