TY - JOUR
T1 - Comparison of Americium(III) and Neodymium(III) Monothiophosphate Complexes
AU - Gomez Martinez, Daniela
AU - Sperling, Joseph M.
AU - Beck, Nicholas B.
AU - Wineinger, Hannah B.
AU - Brannon, Jacob P.
AU - Whitefoot, Megan A.
AU - Horne, Gregory P.
AU - Albrecht-Schönzart, Thomas E.
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/5/20
Y1 - 2024/5/20
N2 - Mixed-donor ligands, such as those containing a combination of O/N or O/S, have been studied extensively for the selective extraction of trivalent actinides, especially Am3+ and Cm3+, from lanthanides during the recycling of used nuclear fuel. Oxygen/sulfur donor ligand combinations also result from the hydrolytic and/or radiolytic degradation of dithiophosphates, such as the Cyanex class of extractants, which are initially converted to monothiophosphates. To understand potential differences between the binding of such degraded ligands to Nd3+ and Am3+, the monothiophosphate complexes [M(OPS(OEt)2)5(H2O)2]2- (M3+ = Nd3+, Am3+) were prepared and characterized by single-crystal X-ray diffraction and optical spectroscopy and studied as a function of pressure up to ca. 14 GPa using diamond-anvil techniques. Although Nd3+ and Am3+ have nearly identical eight-coordinated ionic radii, these structures reveal that while the M-O bond distances in these complexes are almost equal, the M-S distances are statistically different. Moreover, for [Nd(OPS(OEt)2)5(H2O)2]2-, the hypersensitive 4I9/2 → 4G5/2 transition shifts as a function of pressure by −11 cm-1/GPa. Whereas for [Am(OPS(OEt)2)5(H2O)2]2-, the 7F0 → 7F6 transition shows a slightly stronger pressure dependence with a shift of −13 cm-1/GPa and also exhibits broadening of the 5f → 5f transitions at high pressures. These data likely indicate an increased involvement of the 5f orbitals in bonding with Am3+ relative to that of Nd3+ in these complexes.
AB - Mixed-donor ligands, such as those containing a combination of O/N or O/S, have been studied extensively for the selective extraction of trivalent actinides, especially Am3+ and Cm3+, from lanthanides during the recycling of used nuclear fuel. Oxygen/sulfur donor ligand combinations also result from the hydrolytic and/or radiolytic degradation of dithiophosphates, such as the Cyanex class of extractants, which are initially converted to monothiophosphates. To understand potential differences between the binding of such degraded ligands to Nd3+ and Am3+, the monothiophosphate complexes [M(OPS(OEt)2)5(H2O)2]2- (M3+ = Nd3+, Am3+) were prepared and characterized by single-crystal X-ray diffraction and optical spectroscopy and studied as a function of pressure up to ca. 14 GPa using diamond-anvil techniques. Although Nd3+ and Am3+ have nearly identical eight-coordinated ionic radii, these structures reveal that while the M-O bond distances in these complexes are almost equal, the M-S distances are statistically different. Moreover, for [Nd(OPS(OEt)2)5(H2O)2]2-, the hypersensitive 4I9/2 → 4G5/2 transition shifts as a function of pressure by −11 cm-1/GPa. Whereas for [Am(OPS(OEt)2)5(H2O)2]2-, the 7F0 → 7F6 transition shows a slightly stronger pressure dependence with a shift of −13 cm-1/GPa and also exhibits broadening of the 5f → 5f transitions at high pressures. These data likely indicate an increased involvement of the 5f orbitals in bonding with Am3+ relative to that of Nd3+ in these complexes.
UR - https://www.scopus.com/pages/publications/85192845468
U2 - 10.1021/acs.inorgchem.4c00869
DO - 10.1021/acs.inorgchem.4c00869
M3 - Article
C2 - 38722713
AN - SCOPUS:85192845468
SN - 0020-1669
VL - 63
SP - 9237
EP - 9244
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 20
ER -