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 3 publications

(1 citation statement)

References 83 publications

(195 reference statements)

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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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Gas-phase synthesis of [OU–X]⁺ (X = Cl, Br and I) from a UO₂²⁺ precursor using ion-molecule reactions and an [OUCH]⁺ intermediate

Terhorst,

Lenze,

Metzler

et al. 2024

Dalton Trans.

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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 3 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)

Gas-phase synthesis of [OU–X]⁺ (X = Cl, Br and I) from a UO₂²⁺ precursor using ion-molecule reactions and an [OUCH]⁺ intermediate

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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 3 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)

Gas-phase synthesis of [OU–X]+ (X = Cl, Br and I) from a UO22+ precursor using ion-molecule reactions and an [OUCH]+ intermediate

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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)

Gas-phase synthesis of [OU–X]⁺ (X = Cl, Br and I) from a UO₂²⁺ precursor using ion-molecule reactions and an [OUCH]⁺ intermediate