Exploring the Coordination of Plutonium and Mixed Plutonyl–Uranyl Complexes of Imidodiphosphinates

George, K. C.; Muller, Julie; Berthon, Laurence; Berthon, Christophe; Guillaumont, Dominique; Vitórica-Yrezábal, Iñigo J.; Stafford, Hannah; Natrajan, Louise S.; Tamain, Christelle

doi:10.1021/acs.inorgchem.9b00346

Cited by 4 publications

(1 citation statement)

References 83 publications

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“…If we look at Pu(VI) for insights into what we can expect for the range of the plutonyl bond lengths, we find that Pu(VI)–O bond lengths span a wide range from 1.693 to 1.775 Å, and George et al. recently reported an average Pu(VI)–O bond length of 1.739 Å . The Pu(V)–O bond length of 1.876(3) is consistent with this finding as, based simply on oxidation states, we expect the Pu(V)–O bonds to be longer than the Pu(VI)–O bonds.…”

Section: Results and Discussionmentioning

confidence: 99%

Flux Crystal Growth of the Extended Structure Pu(V) Borate Na₂(PuO₂)(BO₃)

et al. 2023

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As part of our exploration of plutonium-containing materials as potential nuclear waste forms, we report the first extended structure Pu(V) material and the first Pu(V) borate. Crystals of Na2(PuO2)(BO3) were grown out of mixed hydroxide/boric acid flux and found to crystallize in the orthorhombic space group Cmcm with lattice parameters of a = 9.9067(4) Å, b = 6.5909(2) Å, and c = 6.9724(2) Å. Na2(PuO2)(BO3) adopts a layered structure in which layers of PuO2(BO3)2– are separated by sodium cations. Plutonium is found in a pentagonal bipyramidal coordination environment, with axial Pu(V)–O plutonyl bond lengths of 1.876(3) Å and equatorial Pu–O bond lengths ranging from 2.325(5) to 2.467(3) Å. We find that the Pu(V)–O plutonyl bond lengths are approximately 0.1 Å longer than the reported Pu(VI)–O plutonyl bond lengths and shorter by approximately 0.033 Å than the corresponding U(V) uranyl bond lengths. Raman spectroscopy on single crystals was used to determine the PuO2 + plutonyl stretching and the equatorial breathing mode frequencies of the pentagonal bipyramidal coordination environment around plutonium. Density functional theory calculations were used to calculate the Raman spectrum to help identify the Raman bands at 690 and 630 cm–1 as corresponding to the plutonyl(V) ν1 stretch and the equatorial PuO5 breathing mode, respectively. UV–vis measurements on single crystals indicate semiconducting behavior with a band gap of ∼2.60 eV.

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Section: Results and Discussionmentioning

confidence: 99%

Flux Crystal Growth of the Extended Structure Pu(V) Borate Na₂(PuO₂)(BO₃)

et al. 2023

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The stability and chemical bonding of a series tridentate ligand-actinyl complexes: [AnO2(L)2]2+ (An: U and Am)

Zhang

Wang

Zhang

et al. 2022

Journal of Molecular Liquids

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Formation of Fully Stoichiometric, Oxidation-State Pure Neptunium and Plutonium Dioxides from Molecular Precursors

Peterson,

Kelly,

Arino

et al. 2024

Inorg. Chem.

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Amidate-based ligands (N-(tert-butyl)isobutyramide, ITA) bind κ 2 to form homoleptic, 8-coordinate complexes with tetravalent 237 Np (Np(ITA) 4 , 1-Np) and 242 Pu (Pu(ITA) 4 , 1-Pu). These compounds complete an isostructural series from Th, U−Pu and allow for the direct comparison between many of the early actinides with stable tetravalent oxidation states by nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction (SCXRD). The molecular precursors are subjected to controlled thermolysis under mild conditions with the exclusion of exogenous air and moisture, facilitating the removal of the volatile organic ligands and ligand byproducts. The preformed metal−oxygen bond in the precursor, as well as the metal oxidation state, are maintained through the decomposition, forming fully stoichiometric, oxidation-state pure NpO 2 and PuO 2 . Powder X-ray diffraction (PXRD), scanning transmission electron microscopy (STEM), and energy dispersive X-ray spectroscopy (EDS) elemental mapping supported the evaluation of these high-purity materials. This chemistry is applicable to a wide range of metals, including actinides, with accessible tetravalent oxidation states, and provides a consistent route to analytical standards of importance to the field of nuclear nonproliferation, forensics, and fundamental studies.

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Exploring the Coordination of Plutonium and Mixed Plutonyl–Uranyl Complexes of Imidodiphosphinates

Abstract: Exploring the coordination of plutonium and mixed plutonyluranyl complexes of imidodiphosphinates.

Cited by 4 publications

References 83 publications

Flux Crystal Growth of the Extended Structure Pu(V) Borate Na₂(PuO₂)(BO₃)

Flux Crystal Growth of the Extended Structure Pu(V) Borate Na₂(PuO₂)(BO₃)

The stability and chemical bonding of a series tridentate ligand-actinyl complexes: [AnO2(L)2]2+ (An: U and Am)

Formation of Fully Stoichiometric, Oxidation-State Pure Neptunium and Plutonium Dioxides from Molecular Precursors

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Exploring the Coordination of Plutonium and Mixed Plutonyl–Uranyl Complexes of Imidodiphosphinates

Abstract: Exploring the coordination of plutonium and mixed plutonyluranyl complexes of imidodiphosphinates.

Cited by 4 publications

References 83 publications

Flux Crystal Growth of the Extended Structure Pu(V) Borate Na2(PuO2)(BO3)

Flux Crystal Growth of the Extended Structure Pu(V) Borate Na2(PuO2)(BO3)

The stability and chemical bonding of a series tridentate ligand-actinyl complexes: [AnO2(L)2]2+ (An: U and Am)

Formation of Fully Stoichiometric, Oxidation-State Pure Neptunium and Plutonium Dioxides from Molecular Precursors

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Flux Crystal Growth of the Extended Structure Pu(V) Borate Na₂(PuO₂)(BO₃)

Flux Crystal Growth of the Extended Structure Pu(V) Borate Na₂(PuO₂)(BO₃)