螯合钚：[Pu(IV){5LIO(Me-3,2-HOPO)}2]——首个结构表征的钚羟基吡啶酮配合物。

Sequestered plutonium: [Pu(IV){5LIO(Me-3,2-HOPO)}2]--the first structurally characterized plutonium hydroxypyridonate complex.

作者信息

Gorden Anne E V, Shuh David K, Tiedemann Bryan E F, Wilson Richard E, Xu Jide, Raymond Kenneth N

机构信息

Glenn T. Seaborg Center, Chemical and Nuclear Sciences Divisions, Lawrence Berkeley, National Laboratory, and Department of Chemistry, University of California, Berkeley, CA 94720-1460, USA.

出版信息

Chemistry. 2005 Apr 22;11(9):2842-8. doi: 10.1002/chem.200401193.

DOI:10.1002/chem.200401193

PMID:15744705

Abstract

The first single-crystal X-ray diffraction analysis of a hydroxypyridonate plutonium(IV) complex is presented, that of the tetradentate ligand 5LIO(Me-3,2-HOPO) with Pu(IV). The [Pu(IV){5LIO(Me-3,2-HOPO)}(2)] complex crystallizes in the space group Pna2(1) with the asymmetric unit cell containing two unique eight-coordinate plutonium complexes and one perchlorate anion. According to shape measure analysis, the geometry of both Pu centers is closest to a bicapped trigonal prism (C(2v) symmetry, for Pu 1: S(C(2v))=13.48 degrees , S(D(4d))=15.43 degrees , S(D(4d))=16.10 degrees ). The average bond length for the Pu--O(phenolic) is 2.31(4) A, whereas the Pu--O(amide) distances are slightly longer, averaging 2.40(2) A. The preparative chemistry of this compound and the implications of the structure are discussed.

摘要

首次报道了一种羟基吡啶酮钚（IV）配合物的单晶X射线衍射分析，即四齿配体5LIO（Me-3,2-HOPO）与Pu（IV）形成的配合物。[Pu（IV）{5LIO（Me-3,2-HOPO）}₂]配合物结晶于空间群Pna2(1)中，不对称晶胞包含两个独特的八配位钚配合物和一个高氯酸根阴离子。根据形状测量分析，两个Pu中心的几何形状最接近双帽三棱柱（C₂ᵥ对称性，对于Pu 1：S（C₂ᵥ） = 13.48°，S（D₄d） = 15.43°，S（D₄d） = 16.10°）。Pu-O（酚羟基）的平均键长为2.31(4) Å，而Pu-O（酰胺基）的距离稍长，平均为2.40(2) Å。讨论了该化合物的制备化学及其结构的意义。