Budantseva Nina, Andreev Grigory, Sokolova Marina, Fedoseev Aleksander
Institute of Physical Chemistry and Electrochemistry, 31 Leninsky pr., 119071, Moscow, Russia.
Inorg Chem. 2021 Dec 6;60(23):18395-18406. doi: 10.1021/acs.inorgchem.1c02991. Epub 2021 Nov 18.
Uranyl compounds with tetrahedral oxoanions demonstrate a significant structural and topological diversity. Complexes of transuranium elements with such anions are not equally well-represented in the literature. To answer the question about the structural similarity in a series of An complexes with XO anions, we synthesized and studied 10 new U, Np, and Pu chromates with outer-sphere organic cations. The structural analysis and comparison with the literature data shows that the Np and Pu complexes are generally based on the same structural blocks as the uranyl compounds. Moreover, the chromate anion does not show any unique structural role as compared to the sulfate and selenate ions. As a result, the neptunium and plutonium chromates contain 1D and 2D structural units similar to those found in the uranyl sulfates and selenates. The templating role of the outer-sphere cations in the actinyl complexes with tetrahedral oxoanions is also not evident, and there is no clear correlation between the nature of the outer-sphere cations and the topology of the structural units.
含四面体含氧阴离子的铀酰化合物展现出显著的结构和拓扑多样性。超铀元素与这类阴离子形成的配合物在文献中的呈现并不均衡。为回答一系列锕系元素与XO阴离子形成的配合物在结构上是否相似这一问题，我们合成并研究了10种带有外球有机阳离子的新型铀、镎和钚的铬酸盐。结构分析以及与文献数据的比较表明，镎和钚的配合物通常与铀酰化合物基于相同的结构单元。此外，与硫酸根和硒酸根离子相比，铬酸根阴离子并未表现出任何独特的结构作用。因此，镎和钚的铬酸盐包含与铀酰硫酸盐和硒酸盐中类似的一维和二维结构单元。外球阳离子在含四面体含氧阴离子的锕酰配合物中的模板作用也不明显，并且外球阳离子的性质与结构单元的拓扑结构之间没有明确的相关性。
