A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, 31 Leninskiy pr., Moscow, 119991, Russia.
Inorg Chem. 2009 Oct 5;48(19):9185-90. doi: 10.1021/ic900710c.
This study concerns the formation of complexes with actinides at oxidation state +IV, from Th to Am, through a lacunary heteropolyanion ligand P(2)W(17)O(61)(10-). The preparation of original single crystals of complexes with 1:2 stoichiometry provided structural data through single-crystal X-ray diffraction for the entire An(IV) series. An(IV) atoms in these complexes have a coordination number of 8, and their coordination polyhedron is a distorted square antiprism. The data were used to compute a mean (An-O) interatomic distance for each actinide. When the interatomic distance is plotted versus the inverse ionic radius of these tetravalent actinides, it appears that the simple electrostatic model is not suitable for Am(IV) and Pu(IV), although this trend must be confirmed by further investigation with other examples from the An(IV) series.
本研究涉及通过缺位杂多阴离子配体 P(2)W(17)O(61)(10-) 形成从 Th 到 Am 的价态为 +IV 的锕系元素配合物。通过单晶 X 射线衍射，用 1:2 化学计量比制备原始单晶配合物，为整个 An(IV)系列提供了结构数据。这些配合物中的 An(IV)原子的配位数为 8，其配位多面体为扭曲的正方形反棱柱体。这些数据用于计算每个锕系元素的平均（An-O）原子间距离。当原子间距离与这些四价锕系元素的反离子半径倒数作图时，表明简单的静电模型不适用于 Am(IV)和 Pu(IV)，尽管这一趋势必须通过进一步研究 An(IV)系列中的其他实例来证实。
