Photochemical separation of plutonium from uranium

DiMucci, Ida M.; Root, Harrison D.; Jones, Zachary R.; Kozimor, Stosh A.; MacInnes, Molly M.; Miller, Jeffrey L.; Mocko, Veronika; Oldham, Warren J.; Stein, Benjamin W.

doi:10.1039/d2cc04225h

Cited by 4 publications

(6 citation statements)

References 31 publications

(41 reference statements)

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“…6 Uranyl( vi ) photolysis can be utilized in two different ways; either to transform U( vi ) into U( iv ) for U recovery, or to reoxidize U( v ) with air and introduce U into a catalytic cycle. 7,8 While photochemical reduction and functionalization of uranyl( vi ) has often been reported in “exotic” systems, here we show that H-abstraction can be performed in a well-controlled manner in mild systems containing only ubiquitous biological substances, such as amino acids and proteins, to which direct C–H to C–C, 3,9 C–O, 10,11 or C–F 12,13 conversion can be applied.…”

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confidence: 64%

“…6 Uranyl(VI) photolysis can be utilized in two different ways; either to transform U(VI) into U(IV) for U recovery, or to reoxidize U(V) with air and introduce U into a catalytic cycle. 7,8 While photochemical reduction and functionalization of uranyl(VI) has often been reported in ''exotic'' systems, here we show that H-abstraction can be performed in a wellcontrolled manner in mild systems containing only ubiquitous biological substances, such as amino acids and proteins, to which direct C-H to C-C, 3,9 C-O, 10,11 or C-F 12,13 conversion can be applied. First, we test our hypothesis that the excited uranyl(VI) aquo ion is a stronger oxidant compared to its coordination complexes, as is indicated by the fact that methanol is readily oxidized by [UO 2 2+ ]* 14 while acetic acid remains intact.…”

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confidence: 64%

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Towards tailoring hydrophobic interaction with uranyl(vi) oxygen for C–H activation

Tsushima,

Kretzschmar,

Doi

et al. 2024

Chem. Commun.

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confidence: 64%

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confidence: 64%

Towards tailoring hydrophobic interaction with uranyl(vi) oxygen for C–H activation

Tsushima,

Kretzschmar,

Doi

et al. 2024

Chem. Commun.

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“…Previous structural studies of plutonium phosphine oxide compounds have focused on Pu(IV) (6 examples) 18−23 and Pu(VI) [as the (Pu VI O 2 ) 2+ ion, 5 examples], 23−26 while no data exist for the Pu(III) ion, despite its accessibility from higher oxidation states in aerobic conditions using chemical or photochemical means. 27,28 Binary Pu IV X 4 (X = Cl, Br) halides are accepted as being unstable relative to the Pu(III/IV) redox couple, as supported by thermodynamic calculations 29 and solution-based evidence. 30,31 This instability has led to the identification of Pu III Br 3 L x (L = solvent) to be an entry point for further Pu(III) chemistry in recent times.…”

Section: ■ Introductionmentioning

confidence: 91%

“…With the general perception that the trans-plutonium elements (Am–Lr) are more “lanthanide like” while the earlier actinides (Ac–Pu) are more “transition metal like”, we turned our attention to plutonium, where increased covalency may further highlight the bonding effects observed in mer -M III Br 3 (OPCy 3 ) 3 . Previous structural studies of plutonium phosphine oxide compounds have focused on Pu(IV) (6 examples) − and Pu(VI) [as the (Pu VI O 2 ) 2+ ion, 5 examples], − while no data exist for the Pu(III) ion, despite its accessibility from higher oxidation states in aerobic conditions using chemical or photochemical means. , …”

Section: Introductionmentioning

confidence: 99%

Stabilization of Pu(IV) in PuBr₄(OPCy₃)₂ and Comparisons with Structurally Similar ThX₄(OPR₃)₂ (R = Cy, Ph) Molecules

Windorff,

Goodwin,

Sperling

et al. 2023

Inorg. Chem.

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The pursuit of a trivalent plutonium halide phosphine oxide compound, e.g., "PuBr 3 (OPR) 3 ," instead led to the isolation of the tetravalent trans-Pu IV Br 4 (OPCy 3 ) 2 , PuBr/ Cy, compound by spontaneous oxidation of Pu III . The donating nature of phosphine oxides has allowed the isolation and characterization of PuBr/Cy by crystallographic, multinuclear NMR, solid state, and solution phase UV−vis-NIR spectroscopic techniques. The presence of a putative plutonyl(VI) complex formulated as "trans-Pu VI O 2 Br 2 (OPCy 3 ) 2 " was also observed spectroscopically and tentatively by single-crystal X-ray diffraction as a cocrystal of PuBr/Cy. A series of trans-ThX 4 (OPCy 3 ) 2 (X = Cl, ThCl/Cy; Br, ThBr/Cy; I, ThI/Cy) complexes were synthesized for comparison to PuBr/Cy. The triphenylphosphine oxide, OPPh 3 , complexes, trans-AnI 4 (OPPh 3 ) 2 (An = Th, ThI/Ph; U, UI/Ph), were also synthesized for comparison, completing the series trans-UX 4 (OPPh 3 ) 2 (X = Cl, Br, I), UX/Ph. To enable the synthesis of ThI/Cy and ThI/Ph, a new nonaqueous thorium iodide starting material, ThI 4 (Et 2 O) 2 , was synthesized. The syntheses of organic solvent soluble ThI 4 L 2 (L = Et 2 O, OPCy 3 , and OPPh 3 ) are the first examples of crystallographically characterized neutral thorium tetraiodide materials beyond binary ThI 4 . To show the viability of ThI 4 (Et 2 O) 2 as a starting material for organothorium chemistry, (C 5 Me 4 H) 3 ThI was synthesized and crystallographically characterized.

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“…The authors have cited additional references within the Supporting Information (Ref. [15,[47][48][49][50][51][52][53][54][55]).…”

Section: Supporting Informationmentioning

confidence: 99%

A New Molybdenum Blue Structure Type: How Uranium Expands this Family of Polyoxometalates

Felton,

Smith,

Poole

et al. 2024

Chemistry A European J

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The assembly of molybdenum polyoxometalates (POMs) has afforded large discrete nanoclusters with varied degrees of reduction such as the ~20% reduced molybdenum blues. While many heterometals have been incorporated into these clusters to afford new properties, uranium has yet to be reported. Here we report the first uranium containing molybdenum blue clusters and the unique properties exhibited by this incorporation. The uranyl ion (UO22+) directs formation of Mo72U8, a square POM comprised of two faces connected by eight edge‐sharing molybdenum dimers. Mo72U8, a chiral cluster, crystallizes as a racemic mixture and, in the solid state, has a ‘negative’ charge localized on one face of the cluster opposite the ‘positively’ charged face of another cluster. Using U(IV) as both heterometal and molybdenum reductant afforded crystals of Mo97U10, a wheel cluster with a heptamolybdate cap on one face. Mo97U10 dissociates in solution, losing the heptamolybdate, to form Mo90U10. Using more solvent during synthesis afforded crystals of Mo90U10S4 which, instead of heptamolybdate, contains four sulfate ions. Crystals of Mo90U10S4 undergo a dehydration induced phase change where clusters form a sheet through oxide bridges. Half of the bridges are cation‐cation interactions between the uranyl oxygen atom and molybdenum, the first reported of this kind.

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Photochemical separation of plutonium from uranium

Abstract: Photochemical reduction and separation of plutonium from uranium in acidic solutions is described as a potential alternative to conventional separations that employ harsh chemical redox agents.

Cited by 4 publications

References 31 publications

Towards tailoring hydrophobic interaction with uranyl(vi) oxygen for C–H activation

Towards tailoring hydrophobic interaction with uranyl(vi) oxygen for C–H activation

Stabilization of Pu(IV) in PuBr₄(OPCy₃)₂ and Comparisons with Structurally Similar ThX₄(OPR₃)₂ (R = Cy, Ph) Molecules

A New Molybdenum Blue Structure Type: How Uranium Expands this Family of Polyoxometalates

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Photochemical separation of plutonium from uranium

Abstract: Photochemical reduction and separation of plutonium from uranium in acidic solutions is described as a potential alternative to conventional separations that employ harsh chemical redox agents.

Cited by 4 publications

References 31 publications

Towards tailoring hydrophobic interaction with uranyl(vi) oxygen for C–H activation

Towards tailoring hydrophobic interaction with uranyl(vi) oxygen for C–H activation

Stabilization of Pu(IV) in PuBr4(OPCy3)2 and Comparisons with Structurally Similar ThX4(OPR3)2 (R = Cy, Ph) Molecules

A New Molybdenum Blue Structure Type: How Uranium Expands this Family of Polyoxometalates

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Stabilization of Pu(IV) in PuBr₄(OPCy₃)₂ and Comparisons with Structurally Similar ThX₄(OPR₃)₂ (R = Cy, Ph) Molecules