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Inorganics 2015, 3(3), 355-369; doi:10.3390/inorganics3030355

Vanadium(V)-Substitution Reactions of Wells–Dawson-Type Polyoxometalates: From [X2M18O62]6 (X = P, As; M = Mo, W) to [X2VM17O62]7

Department of Applied Science, Faculty of Science, Kochi University, Kochi 780-8520, Japan
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Author to whom correspondence should be addressed.
Academic Editors: Greta Ricarda Patzke and Pierre-Emmanuel Car
Received: 14 April 2015 / Revised: 29 May 2015 / Accepted: 25 June 2015 / Published: 14 July 2015
(This article belongs to the Special Issue Polyoxometalates)
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Abstract

The formation processes of V(V)-substituted polyoxometalates with the Wells–Dawson-type structure were studied by cyclic voltammetry and by 31P NMR and Raman spectroscopy. Generally, the vanadium-substituted heteropolytungstates, [P2VW17O62]7 and [As2VW17O62]7, were prepared by mixing equimolar amounts of the corresponding lacunary species—[P2W17O61]10 and [As2W17O61]10—and vanadate. According to the results of various measurements in the present study, the tungsten site in the framework of [P2W18O62]6 and [As2W18O62]6 without defect sites could be substituted with V(V) to form the [P2VW17O62]7 and [As2VW17O62]7, respectively. The order in which the reagents were mixed was observed to be the key factor for the formation of Dawson-type V(V)-substituted polyoxometalates. Even when the concentration of each reagent was identical, the final products differed depending on the order of their addition to the reaction mixture. Unlike Wells–Dawson-type heteropolytungstates, the molybdenum sites in the framework of [P2Mo18O62]6 and [As2Mo18O62]6 were substituted with V(V), but formed Keggin-type [PVMo11O40]4 and [AsVMo11O40]4 instead of [P2VMo17O62]7 and [As2VMo17O62]7, respectively, even though a variety of reaction conditions were used. The formation constant of the [PVMo11O40]4 and [AsVMo11O40]4 was hypothesized to be substantially greater than that of the [P2VMo17O62]7 and [As2VMo17O62]7. View Full-Text
Keywords: polyoxometalate; Wells–Dawson; vanadium; substitution polyoxometalate; Wells–Dawson; vanadium; substitution
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Ueda, T.; Nishimoto, Y.; Saito, R.; Ohnishi, M.; Nambu, J.-I. Vanadium(V)-Substitution Reactions of Wells–Dawson-Type Polyoxometalates: From [X2M18O62]6 (X = P, As; M = Mo, W) to [X2VM17O62]7. Inorganics 2015, 3, 355-369.

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