Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides

Beck, Nicholas B.; Celis-Barros, Cristian; Martelles, Madeline C.; Sperling, Joseph M.; Bai, Zhuanling; Brannon, Jacob P.; Martinez, Daniela Gomez; Huffman, Zachary K.; Long, Brian N.; Mendoza, Kacy N.; Merinsky, Robert W.; Rotermund, Brian M.; Poe, Todd N.; Albrecht, Thomas E.

doi:10.1038/s41467-025-63129-3

Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides

Journal Article · Wed Aug 20 00:00:00 EDT 2025 · Nature Communications

DOI:https://doi.org/10.1038/s41467-025-63129-3· OSTI ID:3003386

^[1]; ^[2]; Martelles, Madeline C. ^[1]; Sperling, Joseph M. ^[1]; ^[1]; ^[1]; Martinez, Daniela Gomez ^[1]; Huffman, Zachary K. ^[3]; Long, Brian N. ^[4]; Mendoza, Kacy N. ^[1]; ^[1]; Rotermund, Brian M. ^[5]; Poe, Todd N. ^[6]; Albrecht, Thomas E. ^[5]

Colorado School of Mines, Golden, CO (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Duke Energy, New Hill, NC (United States). Shearon Harris Nuclear Plant
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Colorado School of Mines, Golden, CO (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

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 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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Colorado School of Mines, Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0012704; SC0023693

OSTI ID:: 3003386

Alternate ID(s):: OSTI ID: 2588517

Report Number(s):: BNL--228910-2025-JAAM

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 16; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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