Structure and Solution Speciation of UIV Linked Phosphomolybdate (MoV) Clusters
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- 作者：Tapash Deb ; Lev Zakharov ; Clément Falaise ; May Nyman
- 刊名：Inorganic Chemistry
- 出版年：2016
- 出版时间：January 19, 2016
- 年：2016
- 卷：55
- 期：2
- 页码：755-761
- 全文大小：424K
- ISSN：1520-510X
文摘
Crystals of [NaU(Mo6P4O31H7)2]·5Na·(H2O)n (NaUMo6) have been synthesized by slow evaporation of an aqueous mixture containing uranyl nitrate, sodium molybdate, phosphoric acid, and sodium dithionate. Single crystal diffraction of NaUMo6 reveals the assembly of {Mo6P4} clusters linked into one-dimensional chains with alternating Na+ and U4+ cations. To our knowledge, NaUMo6 is a unique example of Mo5+ based polyoxometalate associated with actinides. With the use of similar synthesis conditions but without uranium in the aqueous solution, [Na(Mo6P4O31H10)2]·5Na·(H2PO4)·(H2O)n (NaMo6) is obtained. NaMo6 is a sandwich type cluster which is built on the assemblage of two {Mo6P4} units linked by one sodium cation. Using small-angle X-ray scattering techniques and aqueous electrolyte based dissolution strategies, we can accurately observe chains of [UNa(Mo6P4O31H7)2]n5n, where n = 7 is the dominant soluble specie. Likewise, the dimeric form of [Na(Mo6P4O31H10)2]5– dominates the aqueous solution, revealing the structural units observed in the crystal structure are also stable in solution, under appropriate dissolution conditions.