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Variation of the An-O bond lengths in NaAnO2(OOCCH3)3 and (NH4)4AnO2(CO3)3, An = U(VI), Np(VI), and Pu(VI)

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Abstract

For studying actinide contraction in triacetate and tricarbonate complexes of hexavalent actinides in the series U-Np-Pu, single crystals were prepared and crystal structures of NaPuO2(OOCCH3)3 and (NH4)4. AnO2(CO3)3 (An = Np, Pu) were determined. These compounds are isostructural with NaAnO2(OOCCH3)3 (An = U, Np) and (NH4)4UO2(CO3)3 studied previously. The coordination surrounding of An(VI) is a distorted hexagonal bipyramid. The actinide contraction in An(VI) triacetate and tricarbonate complexes is manifested in shortening of the bond lengths in the AnO 2+2 cation in the series U-Np-Pu. In triacetate complexes NaAnO2(OOCCH3)3, the average bond lengths in AnO 2+2 decrease by approximately 2.3% in passing from Np(VI) to Pu(VI). In tricarbonate complexes (NH4)4AnO2(CO3)3, the bond lengths in AnO 2+2 decrease by approximately 0.7% in passing from U to Np and by approximately 0.4% in passing from Np to Pu. The actinide contraction is less noticeable in the equatorial planes of the bipyramids. The lengths of the An-O bonds with oxygen atoms located around actinyl groups depend on the ligand nature and also on participation of oxygen atoms in the coordination with Na+ cations in the triacetate complexes or in hydrogen bonds with NH +4 ions in the tricarbonate complexes.

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Authors and Affiliations

  1. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russia

    I. A. Charushnikova & N. N. Krot

  2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia

    Z. A. Starikova

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  1. I. A. Charushnikova
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  2. N. N. Krot
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  3. Z. A. Starikova
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Original Russian Text © I.A. Charushnikova, N.N. Krot, Z.A. Starikova, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 6, pp. 495–499.

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Charushnikova, I.A., Krot, N.N. & Starikova, Z.A. Variation of the An-O bond lengths in NaAnO2(OOCCH3)3 and (NH4)4AnO2(CO3)3, An = U(VI), Np(VI), and Pu(VI). Radiochemistry 49, 565–570 (2007). https://doi.org/10.1134/S1066362207060033

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  • DOI: https://doi.org/10.1134/S1066362207060033

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