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Complexation-assisted reduction: complexes of glutaroimide-dioxime with tetravalent actinides (Np(iv) and Th(iv))
Zhicheng Zhang1, Bernard F Parker, Trevor D Lohrey
1Chemical Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720, USA. lrao@lbl.gov.
Abstract:
Glutaroimide-dioxime forms strong complexes with tetravalent Th(iv) and Np(iv) in aqueous solution. In conjunction with literature data on the complexation of glutaroimide-dioxime with other metal ions, it was found that the complexes become weaker as the effective charge density on the metal ions decreases: V5+ > Th4+ ≈ Fe3+ > UO22+ > Eu3+/Nd3+ > Cu2+ > Pb2+ > NpO2+ > Ca2+/Mg2+. In the glutaroimide-dioxime complexes with Th(iv) and Np(iv), deprotonation of the imide group and relocation of the two hydrogen atoms from oxygen to nitrogen of the oxime groups result in a large conjugated system (-O-N-C-N-C-N-O-) that coordinates strongly to the metal center in a tridentate mode via the central imide nitrogen atom and the two oxime oxygen atoms. Because the stability of glutaroimide-dioxime complexes with Np(iv) is much higher than those with Np(v), the redox potential of the Np(v)/Np(iv) couple is expected to be shifted significantly. As a result, crystals of glutaroimide-dioxime complexes with Np(iv) were readily obtained from initial solutions containing Np(v). A mechanism of complexation-assisted reduction integrating the thermodynamic and structural data from this work is discussed.
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