Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy
Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy
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DOI：
10.1038/nchem.2692
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发表时间：
2017-06-01
期刊：
影响因子：
21.8
通讯作者：
Mills, David P.
中科院分区：
文献类型：
--
作者：
Formanuik, Alasdair;Ariciu, Ana-Maria;Mills, David P.
我们对锕系元素化学键的了解远远落后于我们对其他系列元素成键机制的理解。这是一个主要问题，因为f区元素在技术和基础上都很重要。锕系元素和镧系元素之间以及不同锕系元素之间的一些关键化学差异可以归因于共价性的微小差异，即f区元素和配位体之间共享电子的程度。然而，几乎没有直接的措施，这种共价锕系元素。本文首次报道了锕系化合物的脉冲电子顺磁共振谱。我们应用超精细次能级相关技术来量化配体核（通过弱超精细相互作用）在分子钍（III）和铀（III）物种的电子自旋密度，因此共价的程度。这些信息对于我们理解锕系元素的化学键以及反应性是很重要的。
Our knowledge of actinide chemical bonds lags far behind our understanding of the bonding regimes of any other series of elements. This is a major issue given the technological as well as fundamental importance of f-block elements. Some key chemical differences between actinides and lanthanides-and between different actinides-can be ascribed to minor differences in covalency, that is, the degree to which electrons are shared between the f-block element and coordinated ligands. Yet there are almost no direct measures of such covalency for actinides. Here we report the first pulsed electron paramagnetic resonance spectra of actinide compounds. We apply the hyperfine sublevel correlation technique to quantify the electron-spin density at ligand nuclei (via the weak hyperfine interactions) in molecular thorium(III) and uranium(III) species and therefore the extent of covalency. Such information will be important in developing our understanding of the chemical bonding, and therefore the reactivity, of actinides.