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Complexation of Eu(III), Am(III) and Cm(III) with Dicarboxylates: Thermodynamics and Structural Aspects of the Binary and Ternary Complexes

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Abstract

The complexation of Eu(III), Am(III) and Cm(III) with dicarboxylate anions with O, N or S donor groups was measured in I=6.60 mol⋅kg−1 (NaClO4) at temperatures of 0–60 °C by potentiometry and solvent extraction. The complexation thermodynamics of these complexes show that their stability is due to highly favorable complexation entropies because the complexation enthalpies are endothermic. Luminescence studies with Eu(III) and Cm(III) were used to measure the hydration numbers of the complexes. NMR spectra of 1H and 13C were used to determine the binding modes of La(III) with the ligands. The formation of 1:1:1 ternary complexes of M(EDTA)− with the dicarboxylate ligands was studied to determine changes in coordination of the metal cation with formation of the ternary species. The complexation of ternary complexes changes from bidentate to monodentate as the chain length between the binding sites of the dicarboxylates increases from 1 (malonate) to 4 (adipate). DFT computations were used to confirm the structural aspects of the interaction of these complexes.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, 32306-4390, USA

    P. Thakur, T. Gedris & G. R. Choppin

  2. Radiochemistry Division, Bhabha Atomic Research Center, Mumbai, India

    P. N. Pathak

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  1. P. Thakur
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  2. P. N. Pathak
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  3. T. Gedris
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  4. G. R. Choppin
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Correspondence to G. R. Choppin.

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Thakur, P., Pathak, P.N., Gedris, T. et al. Complexation of Eu(III), Am(III) and Cm(III) with Dicarboxylates: Thermodynamics and Structural Aspects of the Binary and Ternary Complexes. J Solution Chem 38, 265–287 (2009). https://doi.org/10.1007/s10953-009-9373-8

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