Deviation Between the Chemistry of Ce(IV) and Pu(IV) and Routes to Ordered and Disordered Heterobimetallic 4f/5f and 5f/5f Phosphonates

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• 作者：Juan Diwu ; Shuao Wang ; Justin J. Good ; Victoria H. DiStefano ; Thomas E. Albrecht-Schmitt
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：June 6, 2011
• 年：2011
• 卷：50
• 期：11
• 页码：4842-4850
• 全文大小：1119K
• 年卷期：v.50,no.11(June 6, 2011)
• ISSN：1520-510X

文摘

The heterobimetallic actinide compound UO₂Ce(H₂O)[C₆H₄(PO₃H)₂]₂路H₂O was prepared via the hydrothermal reaction of U(VI) and Ce(IV) in the presence of 1,2-phenylenediphosphonic acid. We demonstrate that this is a kinetic product that is not stable with respect to decomposition to the monometallic compounds. Similar reactions have been explored with U(VI) and Ce(III), resulting in the oxidation of Ce(III) to Ce(IV) and the formation of the Ce(IV) phosphonate, Ce[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]路2H₂O, UO₂Ce(H₂O)[C₆H₄(PO₃H)₂]₂路H₂O, and UO₂[C₆H₄(PO₃H)₂](H₂O)路H₂O. In comparison, the reaction of U(VI) with Np(VI) only yields Np[C₆H₄(PO₃H)₂]₂路2H₂O and aqueous U(VI), whereas the reaction of U(VI) with Pu(VI) yields the disordered U(VI)/Pu(VI) compound, (U_0.9Pu_0.1)O₂[C₆H₄(PO₃H)₂](H₂O)路H₂O, and the Pu(IV) phosphonate, Pu[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]路2H₂O. The reactions of Ce(IV) with Np(VI) yield disordered heterobimetallic phosphonates with both M[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]路2H₂O (M = Ce, Np) and M[C₆H₄(PO₃H)₂]₂路2H₂O (M = Ce, Np) structures, as well as the Ce(IV) phosphonate Ce[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]路2H₂O. Ce(IV) reacts with Pu(IV) to yield the Pu(VI) compound, PuO₂[C₆H₄(PO₃H)₂](H₂O)路3H₂O, and a disordered heterobimetallic Pu(IV)/Ce(IV) compound with the M[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]路2H₂O (M = Ce, Pu) structure. Mixtures of Np(VI) and Pu(VI) yield disordered heterobimetallic Np(IV)/Pu(IV) phosphonates with both the An[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]路2H₂O (M = Np, Pu) and An[C₆H₄(PO₃H)₂]₂路2H₂O (M = Np, Pu) formulas.