Expanding the Crystal Chemistry of Uranyl Peroxides: Four Hybrid Uranyl-Peroxide Structures Containing EDTA

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• 作者：Jie Qiu ; Jie Ling ; Claire Sieradzki ; Kevin Nguyen ; Ernest M. Wylie ; Jennifer E. S. Szymanowski ; Peter C. Burns
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：November 17, 2014
• 年：2014
• 卷：53
• 期：22
• 页码：12084-12091
• 全文大小：523K
• ISSN：1520-510X

文摘

The first four uranyl peroxide compounds containing ethylenediaminetetra-acetate (EDTA) were synthesized and characterized from aqueous uranyl peroxide nitrate solutions with a pH range of 5鈥?. Raman spectra demonstrated that reaction solutions that crystallized [NaK₁₅[(UO₂)₈(O₂)₈(C₁₀H₁₂O₁₀N₂)₂(C₂O₄)₄]路(H₂O)₁₄] (1) and [Li₄K₆[(UO₂)₈(O₂)₆(C₁₀H₁₂O₁₀N₂)₂(NO₃)₆]路(H₂O)₂₆] (2) contained excess peroxide, and their structures contained oxidized ethylenediaminetetraacetate, EDTAO₂^{4鈥?/sup>. The solutions from which [K₄[(UO₂)₄(O₂)₂(C₁₀H₁₃O₈N₂)₂(IO₃)₂]路(H₂O)₁₆] (3) and LiK₃[(UO₂)₄(O₂)₂(C₁₀H₁₂O₈N₂)₂(H₂O)₂]路(H₂O)₁₈ (4) crystallized contained no free peroxide, and the structures incorporated intact EDTA4鈥?/sup>. In contrast to the large family of uranyl peroxide cage clusters, coordination of uranyl peroxide units in 1鈥?b>4 by EDTA4鈥?/sup> or EDTAO₂4鈥?/sup> results in isolated tetramers or dimers of uranyl ions that are bridged by bidentate peroxide groups. Two tetramers are bridged by EDTAO₂4鈥?/sup> to form octamers in 1 and 2, and dimers of uranyl polyhedra are linked through iodate groups in 3 and EDTA4鈥?/sup> in 4, forming chains in both cases. In each structure the U鈥揙₂鈥揢 dihedral angle is strongly bent, at 鈭?40掳, consistent with the configuration of this linkage in cage clusters and other recently reported uranyl peroxides.}