Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 19, Issue 16, Pages 5191-5197Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201204563
Keywords
niobium; NMR spectroscopy; phosphorus; polyoxometalates; vanadium
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Funding
- NSF CCI grant through the Center for Sustainable Materials Chemistry [CHE-1102637]
- Australian Research Council [DP110105530]
- NSF
- Alfred P. Sloan Minority Ph.D. Program
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1102637] Funding Source: National Science Foundation
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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 31P and 51V 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.
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