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Inorganics 2015, 3(3), 355-369;

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
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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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

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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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