Strongly coupled binuclear uranium-oxo complexes from uranyl oxo rearrangement and reductive silylation
Strongly coupled binuclear uranium-oxo complexes from uranyl oxo rearrangement and reductive silylation
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DOI：
10.1038/nchem.1270
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发表时间：
2012-03-01
期刊：
影响因子：
21.8
通讯作者：
Love, Jason B.
中科院分区：
文献类型：
--
作者：
Arnold, Polly L.;Jones, Guy M.;Love, Jason B.
铀化学中最常见的基序是d（0）f（0）铀酰离子[UO 2]（2+），其中氧代基团是严格线性和惰性的。替代的几何形状，如顺式铀酰，已被确定在理论上和牵连的氧原子转移反应，是相关的环境形态和核废料修复。现在已知单电子还原赋予更大的氧代基团反应性，但保留线性OUO基序，并且氧代基团形成新共价键的反应仍然罕见。在这里，我们描述了一个双核铀氧配合物的合成，结构，反应性和磁性。这种新的蝶形Si-OUO_2UO_Si分子是通过还原、硅氧加成以及反式到顺式的迁移而形成的，具有很强的U-V-U-V耦合和化学惰性，表明这种重排的铀氧基序可能存在于环境中的其他锕系元素中，并与锕系氧化物簇的聚集有关。
The most common motif in uranium chemistry is the d(0)f(0) uranyl ion [UO2](2+) in which the oxo groups are rigorously linear and inert. Alternative geometries, such as the cis-uranyl, have been identified theoretically and implicated in oxo-atom transfer reactions that are relevant to environmental speciation and nuclear waste remediation. Single electron reduction is now known to impart greater oxo-group reactivity, but with retention of the linear OUO motif, and reactions of the oxo groups to form new covalent bonds remain rare. Here, we describe the synthesis, structure, reactivity and magnetic properties of a binuclear uranium-oxo complex. Formed through a combination of reduction and oxo-silylation and migration from a trans to a cis position, the new butterfly-shaped Si-OUO2UO-Si molecule shows remarkably strong U-V-U-V coupling and chemical inertness, suggesting that this rearranged uranium oxo motif might exist for other actinide species in the environment, and have relevance to the aggregation of actinide oxide clusters.