TY - JOUR
T1 - Cocrystallization of Plutonium(III) and Plutonium(IV) Diglycolamides with Pu(III) and Pu(IV) Hexanitrato Anions
T2 - A Route to Redox Variants of [PuIII,IV(DGA)3]x+
AU - Rotermund, Brian M.
AU - Sperling, Joseph M.
AU - Horne, Gregory P.
AU - Beck, Nicholas B.
AU - Wineinger, Hannah B.
AU - Bai, Zhuanling
AU - Celis-Barros, Cristian
AU - Gomez Martinez, Daniela
AU - Albrecht-Schönzart, Thomas E.
N1 - Funding Information:
This work was supported by the U.S. Department of Energy (DOE), Office of Sciences, Office of Basic Energy Sciences, Solar Photochemistry Program award DE-SC0021372.
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/7/31
Y1 - 2023/7/31
N2 - N,N,N′,N’-tetramethyl diglycolamide (TMDGA), a methylated variant of the diglycolamide extractants being proposed as curium holdback reagents in advanced used nuclear fuel reprocessing technologies, has been crystallized with plutonium, a transuranic actinide that has multiple accessible oxidation states. Two plutonium TMDGA complexes, [PuIII(TMDGA)3][PuIII(NO3)6] and[PuIV(TMDGA)3][PuIV(NO3)6]2·0.75MeOH, were crystallized through solvent diffusion of a reaction mixture containing plutonium(III) nitrate and TMDGA. The sample was then partially oxidized by air to yield [PuIV(TMDGA)3][PuIV(NO3)6]2·0.75MeOH. Single-crystal X-ray diffraction reveals that the multinuclear systems crystallize with hexanitrato anionic species, providing insight into the first solid-state isolation of the elusive trivalent plutonium hexanitrato species. Crystallography data show a change in geometry around the TMDGA metal center from Pu3+ to Pu4+, with the symmetry increasing approximately from C4v to D3h. These complexes provide a rare opportunity to investigate the bond metrics of plutonium in two different oxidation states with similar coordination environments. Further, these new structures provide insight into the potential chemical and structural differences arising from the radiation-induced formation of transient tetravalent curium oxidation states in used nuclear fuel reprocessing streams.
AB - N,N,N′,N’-tetramethyl diglycolamide (TMDGA), a methylated variant of the diglycolamide extractants being proposed as curium holdback reagents in advanced used nuclear fuel reprocessing technologies, has been crystallized with plutonium, a transuranic actinide that has multiple accessible oxidation states. Two plutonium TMDGA complexes, [PuIII(TMDGA)3][PuIII(NO3)6] and[PuIV(TMDGA)3][PuIV(NO3)6]2·0.75MeOH, were crystallized through solvent diffusion of a reaction mixture containing plutonium(III) nitrate and TMDGA. The sample was then partially oxidized by air to yield [PuIV(TMDGA)3][PuIV(NO3)6]2·0.75MeOH. Single-crystal X-ray diffraction reveals that the multinuclear systems crystallize with hexanitrato anionic species, providing insight into the first solid-state isolation of the elusive trivalent plutonium hexanitrato species. Crystallography data show a change in geometry around the TMDGA metal center from Pu3+ to Pu4+, with the symmetry increasing approximately from C4v to D3h. These complexes provide a rare opportunity to investigate the bond metrics of plutonium in two different oxidation states with similar coordination environments. Further, these new structures provide insight into the potential chemical and structural differences arising from the radiation-induced formation of transient tetravalent curium oxidation states in used nuclear fuel reprocessing streams.
UR - http://www.scopus.com/inward/record.url?scp=85167790821&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/c314ad41-8b0d-3601-9268-383c74de210d/
U2 - 10.1021/acs.inorgchem.3c01590
DO - 10.1021/acs.inorgchem.3c01590
M3 - Article
AN - SCOPUS:85167790821
SN - 0020-1669
VL - 62
SP - 12905
EP - 12912
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 32
ER -