Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions
Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions
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DOI：
10.1038/nchem.2767
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发表时间：
2017-09-01
期刊：
影响因子：
21.8
通讯作者：
Bart, Suzanne C.
中科院分区：
文献类型：
--
作者：
Anderson, Nickolas H.;Xie, Jing;Bart, Suzanne C.
锕基物质[AnO（2）]（2+）是众所周知的f区衍生物，因为它们在核燃料循环中的自然存在和重要作用。沿着它们的氮类似物[An（NR）（2）]（2+），actinyls的特征在于它们的两个强的反式An-元素多重键，这是反式影响的结果。我们报道了这些强键可以通过增加与铀的多重键的数量而显著减弱，如具有四个U-N多重键的铀（VI）二价阴离子家族[M]（2）[U（NR）（4）]（M=Li，Na，K，Rb，Cs）所证明的。它们的几何形状是由阳离子配位和空间位阻决定的，而不是电子因素。通过加入强π供体来削弱多重键具有在处理高价actinyls中应用的潜力，高价actinyls通常存在于环境污染物和乏核燃料中。
Actinyl species, [AnO(2)](2+), are well-known derivatives of the f-block because of their natural occurrence and essential roles in the nuclear fuel cycle. Along with their nitrogen analogues, [An(NR)(2)](2+), actinyls are characterized by their two strong trans-An-element multiple bonds, a consequence of the inverse trans influence. We report that these robust bonds can be weakened significantly by increasing the number of multiple bonds to uranium, as demonstrated by a family of uranium(VI) dianions bearing four U-N multiple bonds, [M](2)[U(NR)(4)] (M=Li, Na, K, Rb, Cs). Their geometry is dictated by cation coordination and sterics rather than by electronic factors. Multiple bond weakening by the addition of strong pi donors has the potential for applications in the processing of high-valent actinyls, commonly found in environmental pollutants and spent nuclear fuels.