Tetraalkylammonium uranyl isothiocyanates.
Tetraalkylammonium uranyl isothiocyanates.
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DOI：
10.1021/ic301741u
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发表时间：
2012-11
影响因子：
4.6
通讯作者：
Clare E Rowland;Mercouri G Kanatzidis;L. Soderholm
中科院分区：
文献类型：
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作者：
Clare E Rowland;Mercouri G Kanatzidis;L. Soderholm
从水溶液中合成了三种四烷基铀酰异硫氰酸铵[（CH（3））（4）N]（3）UO（2）（NCS）（5）（1），[（C（2）H（5））（4）N]（3）UO（2）（NCS）（5）（2）和[（C（3）H（7））（4）N]（3）UO（2）（NCS）（5）（3），用单晶X射线衍射法测定了它们的结构。所有化合物均由铀酰阳离子与五个N-结合的硫氰酸盐配体UO（2）（NCS）（5）（3-）赤道配位组成，并由三个四烷基铵阳离子进行电荷平衡。拉曼光谱数据已收集的化合物1-3，以及对溶液的硝酸铀酰与硫氰酸钠的水平增加。通过跟踪硫氰酸盐的拉曼特征，证实溶液中存在游离和结合的硫氰酸盐。铀酰对称伸缩模的拉曼信号的位移表明在溶液中形成了更高阶的铀酰硫氰酸盐络合物，而固态拉曼数据支持关于铀酰阳离子的均配异硫氰酸盐配位。本文介绍了1-3的合成和晶体结构，有关的拉曼光谱，并讨论了这些异硫氰酸酯与前面所述的卤化铀酰相UO（2）X（4）（2-）的关系。
Three tetraalkylammonium uranyl isothiocyanates, [(CH(3))(4)N](3)UO(2)(NCS)(5) (1), [(C(2)H(5))(4)N](3)UO(2)(NCS)(5) (2), and [(C(3)H(7))(4)N](3)UO(2)(NCS)(5) (3), have been synthesized from aqueous solution and their structures determined by single-crystal X-ray diffraction. All of the compounds consist of the uranyl cation equatorially coordinated to five N-bound thiocyanate ligands, UO(2)(NCS)(5)(3-), and charge-balanced by three tetraalkylammonium cations. Raman spectroscopy data have been collected on compounds 1-3, as well as on solutions of uranyl nitrate with increasing levels of sodium thiocyanate. By tracking the Raman signatures of thiocyanate, the presence of both free and bound thiocyanate is confirmed in solution. The shift in the Raman signal of the uranyl symmetric stretching mode suggests the formation of higher-order uranyl thiocyanate complexes in solution, while the solid-state Raman data support homoleptic isothiocyanate coordination about the uranyl cation. Presented here are the syntheses and crystal structures of 1-3, pertinent Raman spectra, and a discussion regarding the relationship of these isothiocyanates to previously described uranyl halide phases, UO(2)X(4)(2-).