锕系元素膦酸盐的周期性趋势：钍、铀、镎和钚体系之间的差异与趋同

Periodic trends in actinide phosphonates: divergence and convergence between thorium, uranium, neptunium, and plutonium systems.

作者信息

Nelson Anna-Gay D, Bray Travis H, Stanley Forrest A, Albrecht-Schmitt Thomas E

机构信息

Department of Civil Engineering and Geological Sciences, University of Notre Dame, Notre Dame, Indiana 46556-9956, USA.

出版信息

Inorg Chem. 2009 May 18;48(10):4530-5. doi: 10.1021/ic900484w.

DOI:10.1021/ic900484w

PMID:19348443

Abstract

The hydrothermal reactions of both PuO(2)(2+) and PuO(2) with phosphonates results in the formation of Pu(IV) phosphonates. Pu(CH(3)PO(3))(2), PuCH(2)(PO(3))(2), and UO(2)Pu(H(2)O)(2)CH(2)(PO(3))(PO(3)H) have been isolated from these reactions and structurally characterized. Pu(CH(3)PO(3))(2) contains six-coordinate Pu(IV) and adopts a structure closely related to that of alpha-Zr(HPO(4))(2). PuCH(2)(PO(3))(2) forms a novel three-dimensional network with seven-coordinate Pu(IV) and chelating/bridging CH(2)(PO(3))(2) anions. The heterobimetallic U(VI)/Pu(IV) diphosphonate, UO(2)Pu(H(2)O)(2)CH(2)(PO(3))(PO(3)H), also forms a three-dimensional network. To complete the AnCH(2)(PO(3))(2)(n) (An = Th, U, Np, Pu; n = 1, 2) and UO(2)An(H(2)O)(2)CH(2)(PO(3))(PO(3)H) series, ThCH(2)(PO(3))(2)(2) and UO(2)Th(H(2)O)(2)CH(2)(PO(3))(PO(3)H) have also been prepared. These compounds are isostructural with their Np(IV) analogues.

摘要

二氧化钚（IV）离子（PuO(2)(2+)）和二氧化钚（PuO(2)）与膦酸盐发生水热反应，生成钚（IV）膦酸盐。已从这些反应中分离出 Pu(CH(3)PO(3))(2)、PuCH(2)(PO(3))(2) 和 UO(2)Pu(H(2)O)(2)CH(2)(PO(3))(PO(3)H)，并对其进行了结构表征。Pu(CH(3)PO(3))(2) 含有六配位的钚（IV），其结构与 α-Zr(HPO(4))(2) 密切相关。PuCH(2)(PO(3))(2) 形成一种新型的三维网络结构，其中钚（IV）为七配位，CH(2)(PO(3))(2) 阴离子起螯合/桥连作用。异双金属的 U(VI)/Pu(IV) 二膦酸盐 UO(2)Pu(H(2)O)(2)CH(2)(PO(3))(PO(3)H) 也形成三维网络结构。为完善 AnCH(2)(PO(3))(2)(n)（An = Th、U、Np、Pu；n = 1、2）和 UO(2)An(H(2)O)(2)CH(2)(PO(3))(PO(3)H) 系列，还制备了 ThCH(2)(PO(3))(2)(2) 和 UO(2)Th(H(2)O)(2)CH(2)(PO(3))(PO(3)H)。这些化合物与其 Np(IV) 类似物具有同构结构。