Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Inorg Chem. 2011 Jun 20;50(12):5663-70. doi: 10.1021/ic200384h. Epub 2011 May 18.
The chemistry of tetravalent Pu with sulfate is explored in a series of single-crystal X-ray diffraction studies of the alkali metal plutonium sulfate compounds. Five new structures of Pu(IV) sulfates are presented including the structure for the α-phase of Pu(SO(4))(2)(H(2)O)(4), Na(10)Pu(2)(SO(4))(9)(H(2)O)(4), K(8)Pu(2)(SO(4))(8)(H(2)O)(5), Rb(8)Pu(2)(SO(4))(8)(H(2)O)(4), and Cs(4)Pu(SO(4))(4)(H(2)O)(2). Changes in structure and stoichiometry are seen down the alkali-metal series despite identical reaction conditions for each of the complexes. Comparison to the other known An(IV) sulfates, Group IV sulfates, and Ce(IV) reveals limited similarity in stoichiometry and structure across the actinide series and their homologues. Marked color changes are observed down the series indicating strong interactions between the plutonium ions and the ligands in these complexes.
本文通过一系列的碱金属钚硫酸盐化合物的单晶 X 射线衍射研究，探讨了四价钚与硫酸盐的化学性质。介绍了 5 种新的 Pu(IV)硫酸盐结构，包括α-相 Pu(SO(4))(2)(H(2)O)(4)、Na(10)Pu(2)(SO(4))(9)(H(2)O)(4)、K(8)Pu(2)(SO(4))(8)(H(2)O)(5)、Rb(8)Pu(2)(SO(4))(8)(H(2)O)(4)和 Cs(4)Pu(SO(4))(4)(H(2)O)(2)的结构。尽管每个配合物的反应条件相同，但在碱金属系列中观察到结构和化学计量的变化。与其他已知的 An(IV)硫酸盐、IV 族硫酸盐和 Ce(IV)的比较表明，在锕系元素及其同系物中，化学计量和结构的相似性有限。在整个系列中观察到明显的颜色变化，表明这些配合物中钚离子与配体之间存在强烈的相互作用。
