A Soluble Phosphorus-Centered Keggin Polyoxoniobate with Bicapping Vanadyl Groups

Authors

  • Dr. Jung-Ho Son,

    1. Department of Chemistry, University of California, Davis, One Shields Ave. Davis, CA 95616 (USA), Fax: (+1) 530-752 8995
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  • Dr. C. André Ohlin,

    1. School of Chemistry, Monash University, Victoria 3800 (Australia)
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  • Rene L. Johnson,

    1. Department of Chemistry, University of California, Davis, One Shields Ave. Davis, CA 95616 (USA), Fax: (+1) 530-752 8995
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  • Dr. Ping Yu,

    1. Keck NMR Facility, University of California, Davis, One Shields Ave. Davis, CA 95616 (USA)
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  • Prof. William H. Casey

    Corresponding author
    1. Department of Chemistry, University of California, Davis, One Shields Ave. Davis, CA 95616 (USA), Fax: (+1) 530-752 8995
    2. Department of Geology, University of California, Davis, One Shields Ave. Davis, CA 95616 (USA)
    • Department of Chemistry, University of California, Davis, One Shields Ave. Davis, CA 95616 (USA), Fax: (+1) 530-752 8995
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Abstract

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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