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Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides
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Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides
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Journal Article
Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides
2025
Overview
The trivalent actinides are produced in the nuclear fuel cycle during power production and provide the largest long-term radiation dose in used nuclear fuel. It is ideal for these elements to be removed from used nuclear fuel for disposal and a necessity for fuel recycling. A key challenge to this is the similarity of chemical behavior of the trivalent actinides to the lanthanides that are also present as fission products in used fuel. Thus far, some of the most effective separations of actinides from lanthanides utilise chelating agents containing sulfur moieties such as dithiophosphinates that selectively bind to actinide ions because of a greater bond covalency relative to lanthanide ions. Typically, greater differences between actinide and lanthanide ions are observable the more ligands and chelators bonds have a covalent character. Here, a series of complexes of the trivalent actinides Np(III) through Cf(III) (excluding Bk(III)) with maleonitrile-1,2-dithiolate (mnt
2–
) are synthesized along with their lanthanide counterparts (La(III) – Nd(III), Sm(III) – Gd(III), Dy(III)), in order to characterize the nature of chemical bonds with these metal ions and a polarizable, non-innocent, sulfur-donor ligand. The metal-sulfur bonds in these complexes trend shorter than measured for lanthanides with equivalent ionic radii. However, particularly large deviations are observed in the neptunium and plutonium complexes in both structure and bonding, resulting in a nonlinear bond length trendline for the actinide series. Density Functional Theory (DFT) calculations with Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Order (NBO) analyses indicate that for the neptunium and plutonium complexes, the presence of increased 5
f
-orbital participation, energy degeneracy of the metal and ligand orbitals, and the structure packing result in shortened M–S bonds. The stabilization of the energy of the 5
f
-orbitals and the decrease in
f
-contribution to bonding orbitals in the later actinides results in structural properties more similar to the lanthanide complexes.
Although the trivalent actinides are similar to the lanthanide series in terms of chemistry and bonding, their structures and properties can diverge significantly. Here, the authors report a series of complexes of the trivalent actinides Np(III) through Cf(III) along with their lanthanide counterparts using a polarizable non-innocent, sulfur-donor ligand.
Publisher
Nature Publishing Group UK,Nature Publishing Group,Springer Science and Business Media LLC,Nature Portfolio
