Abstract <p>The results of studying the interaction of An(III–VI) with 2,6- pyridinedicarboxylic acid (2,6-PDCA) are summarized. The stability constants are estimated for complexes An<sup>IV</sup>(PDC)<sub><i>n</i></sub><sup>4–2<i>n</i></sup> (<i>n</i> = 1–3). The total stability constant exceeds 10<sup>25</sup> mol<sup>–3</sup> L<sup>–3</sup> and increases in the series from Th(IV) to Pu(IV) by 8 orders of magnitude. The difference in the stability of the An(III) and An(IV) complexes leads to rapid oxidation of Pu(III) to Pu(IV) with oxygen in the presence of 2,6-PDCA. An(V) and An(VI) ions form 1 : 1 and 1 : 2 complexes with PDC. The formation of An(IV,V,VI) complexes leads to a shift in the redox potential of the (V)/(IV) and (VI)/(V) couples. An(V) disproportionate in the presence of 2,6-PDCA anions. For An(VI) complexes of 1 : 2 composition, the <i>f</i>–<i>f</i> transition bands are weakened, which is associated with the centrosymmetrical structure of the coordination polyhedron of the An atom. The stability of the An(VI) complexes was evaluated. An(III) ions form compounds with PDC<sup>2–</sup> in which the metal : ligand ratio is 1 : 3. Compounds An<sup>IV</sup>(PDC)<sub>2</sub> and those with an anionic moiety in the form of An<sup>IV</sup>(PDC)<sub>3</sub><sup>2–</sup> were obtained. The cations were imidazole, Cs<sup>+</sup>, Ln<sup>2+</sup>, and Ln<sup>3+</sup>. An(V) forms compounds with one and two PDC<sup>2–</sup> ions. Compounds of UO<sub>2</sub><sup>2+</sup> with PDC<sup>2–</sup>, as well as UO<sub>2</sub>(PDC)<sub>2</sub><sup>2–</sup> compounds with organic and inorganic outer-sphere cations have been studied. According to X-ray diffraction analysis, the AnO<sub>2</sub>(PDC)<sub>2</sub><sup>2–</sup> have the center of symmetry. In the isostructural series [Li<sub>2</sub>AnO<sub>2</sub>(PDC)<sub>2</sub>]·2H<sub>2</sub>O, actinide contraction is expressed in a decrease in the An=O distances in the “yl” groups from U to Pu. In all cases, PDC<sup>2–</sup> is coordinated in the tridentate fashion through two oxygen atoms of carboxyl groups and a nitrogen atom.</p>

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Reactions of Actinide Ions with 2,6-Pyridinedicarboxylic Acid in Aqueous Solutions and the Structure of Crystalline Compounds

  • B. F. Myasoedov,
  • A. M. Fedoseev,
  • V. P. Shilov

摘要

Abstract

The results of studying the interaction of An(III–VI) with 2,6- pyridinedicarboxylic acid (2,6-PDCA) are summarized. The stability constants are estimated for complexes AnIV(PDC)n4–2n (n = 1–3). The total stability constant exceeds 1025 mol–3 L–3 and increases in the series from Th(IV) to Pu(IV) by 8 orders of magnitude. The difference in the stability of the An(III) and An(IV) complexes leads to rapid oxidation of Pu(III) to Pu(IV) with oxygen in the presence of 2,6-PDCA. An(V) and An(VI) ions form 1 : 1 and 1 : 2 complexes with PDC. The formation of An(IV,V,VI) complexes leads to a shift in the redox potential of the (V)/(IV) and (VI)/(V) couples. An(V) disproportionate in the presence of 2,6-PDCA anions. For An(VI) complexes of 1 : 2 composition, the ff transition bands are weakened, which is associated with the centrosymmetrical structure of the coordination polyhedron of the An atom. The stability of the An(VI) complexes was evaluated. An(III) ions form compounds with PDC2– in which the metal : ligand ratio is 1 : 3. Compounds AnIV(PDC)2 and those with an anionic moiety in the form of AnIV(PDC)32– were obtained. The cations were imidazole, Cs+, Ln2+, and Ln3+. An(V) forms compounds with one and two PDC2– ions. Compounds of UO22+ with PDC2–, as well as UO2(PDC)22– compounds with organic and inorganic outer-sphere cations have been studied. According to X-ray diffraction analysis, the AnO2(PDC)22– have the center of symmetry. In the isostructural series [Li2AnO2(PDC)2]·2H2O, actinide contraction is expressed in a decrease in the An=O distances in the “yl” groups from U to Pu. In all cases, PDC2– is coordinated in the tridentate fashion through two oxygen atoms of carboxyl groups and a nitrogen atom.