Facile Routes to ThIV, UIV, and NpIV Phosphites and Phosphates
Facile Routes to ThIV, UIV, and NpIV Phosphites and Phosphates
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ThIV、UIV 和 NpIV 磷酸盐和磷酸盐的简便途径
DOI：
10.1002/ejic.201100464
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发表时间：
2011
影响因子：
2.3
通讯作者：
T. Albrecht‐Schmitt
中科院分区：
文献类型：
--
作者：
E. Villa;Shuao Wang;E. Alekseev;W. Depmeier;T. Albrecht‐Schmitt
采用温和的水热条件合成了三种锕系亚磷酸盐和一种Np（IV）磷酸盐An（IV）（HPO（3））（2）（H（2）O）（2）（An = Th，U，Np）和Cs[Np（H（1.5）PO（4））（PO（4））]（2）。前三相是同型的，并且使用类似的反应条件获得。Cs[Np（H（1.5）PO（4））（PO（4））]（2）的合成采用与Np（HPO（3））（2）（H（2）O）（2）类似的方法。然而，这第四相在组成和结构上与其他相相比是完全不同的。Cs[Np（H（1.5）PO（4））（PO（4））]（2）的结构是由磷酸镎（IV）与层间区域的铯阳离子构成的双层结构。与此相反，An（HPO（3））（2）（H（2）O）（2）（An = Th，U，Np）形成密集的三维网络。从单晶X射线衍射数据获得的各种度量中检测到的锕系收缩。镎起始材料氧化态的变化产生不同的产物。
Three actinide(IV) phosphites and a Np(IV) phosphate, An(IV)(HPO(3))(2)(H(2)O)(2) (An = Th, U, Np) and Cs[Np(H(1.5)PO(4))(PO(4))](2), respectively, were synthesized using mild hydrothermal conditions. The first three phases are isotypic and were obtained using similar reaction conditions. Cs[Np(H(1.5)PO(4))(PO(4))](2) was synthesized using an analogous method to that of Np(HPO(3))(2)(H(2)O)(2). However, this fourth phase is quite different in comparison to the other phases in both composition and structure. The structure of Cs[Np(H(1.5)PO(4))(PO(4))](2) is constructed from double layers of neptunium(IV) phosphate with caesium cations in the interlayer region. In contrast, An(HPO(3))(2)(H(2)O)(2) (An = Th, U, Np) form dense 3D networks. The actinide contraction is detected in variety of metrics obtained from single-crystal X-ray diffraction data. Changes in the oxidation state of the neptunium starting materials yield different products.