Uranyl oxo activation and functionalization by metal cation coordination
Uranyl oxo activation and functionalization by metal cation coordination
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DOI：
10.1038/nchem.904
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发表时间：
2010-12-01
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.;Pecharman, Anne-Frederique;Love, Jason B.
铀酰离子[UO2](2+)中的氧基团是由元素周期表中的金属形成的许多氧基阳离子之一，它是特别惰性的，这解释了这种离子在实验室中的主导地位及其作为环境污染物的持久性。相反，过渡金属氧(M=O)化合物可以是高活性的，并执行困难的反应，如碳氢化合物的氧化。在这里，我们展示了在‘Pacman’环境下，锂金属碱与铀酰离子的顺序加成是如何导致锂与U=O键配位和单电子还原的。这一反应取决于锂试剂的性质和化学计量比，表明正在发生竞争还原和C-H键活化反应。
The oxo groups in the uranyl ion [UO2](2+)-one of many oxo cations formed by metals from across the periodic table-are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring.