Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides
Abstract 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...
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Nature Portfolio
2025-08-01
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| Online Access: | https://doi.org/10.1038/s41467-025-63129-3 |
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| author | Nicholas B. Beck Cristian Celis-Barros Madeline C. Martelles Joseph M. Sperling Zhuanling Bai Jacob P. Brannon Daniela Gomez Martinez Zachary K. Huffman Brian N. Long Kacy N. Mendoza Robert W. Merinsky Brian M. Rotermund Todd N. Poe Thomas E. Albrecht |
| author_facet | Nicholas B. Beck Cristian Celis-Barros Madeline C. Martelles Joseph M. Sperling Zhuanling Bai Jacob P. Brannon Daniela Gomez Martinez Zachary K. Huffman Brian N. Long Kacy N. Mendoza Robert W. Merinsky Brian M. Rotermund Todd N. Poe Thomas E. Albrecht |
| author_sort | Nicholas B. Beck |
| collection | DOAJ |
| description | Abstract 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 (mnt2–) 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 5f-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 5f-orbitals and the decrease in f-contribution to bonding orbitals in the later actinides results in structural properties more similar to the lanthanide complexes. |
| format | Article |
| id | doaj-art-fe688dc97af4490d88ab5ec8776e3aed |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-08-01 |
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| spelling | doaj-art-fe688dc97af4490d88ab5ec8776e3aed2025-08-24T11:38:01ZengNature PortfolioNature Communications2041-17232025-08-0116111110.1038/s41467-025-63129-3Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinidesNicholas B. Beck0Cristian Celis-Barros1Madeline C. Martelles2Joseph M. Sperling3Zhuanling Bai4Jacob P. Brannon5Daniela Gomez Martinez6Zachary K. Huffman7Brian N. Long8Kacy N. Mendoza9Robert W. Merinsky10Brian M. Rotermund11Todd N. Poe12Thomas E. Albrecht13Colorado School of MinesOak Ridge National LaboratoryColorado School of MinesColorado School of MinesColorado School of MinesColorado School of MinesColorado School of MinesDuke Energy, Shearon Harris Nuclear PlantLos Alamos National LaboratoryColorado School of MinesColorado School of MinesColorado School of MinesBrookhaven National LaboratoryColorado School of MinesAbstract 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 (mnt2–) 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 5f-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 5f-orbitals and the decrease in f-contribution to bonding orbitals in the later actinides results in structural properties more similar to the lanthanide complexes.https://doi.org/10.1038/s41467-025-63129-3 |
| spellingShingle | Nicholas B. Beck Cristian Celis-Barros Madeline C. Martelles Joseph M. Sperling Zhuanling Bai Jacob P. Brannon Daniela Gomez Martinez Zachary K. Huffman Brian N. Long Kacy N. Mendoza Robert W. Merinsky Brian M. Rotermund Todd N. Poe Thomas E. Albrecht Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides Nature Communications |
| title | Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides |
| title_full | Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides |
| title_fullStr | Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides |
| title_full_unstemmed | Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides |
| title_short | Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides |
| title_sort | non linear bonding trends in maleonitrile 1 2 dithiolate complexes of the transuranium actinides |
| url | https://doi.org/10.1038/s41467-025-63129-3 |
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