Stabilization of Plutonium(V) Within a Crown Ether Inclusion Complex

Wang, Yaxing; Hu, Shu‐Xian; Cheng, Liwei; Liang, Chengyu; Yin, Xuemiao; Zhang, Hailong; Li, Ao; Sheng, Daopeng; Diwu, Juan; Wang, Xiaolin; Li, Jun; Chai, Zhifang; Wang, Shuao

doi:10.31635/ccschem.020.202000152

Cited by 40 publications

(31 citation statements)

References 13 publications

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“…In contrast, the gauche conformation is observed in [Pu(H 2 O) 4 (18-crown-6)] 3+ units, which may be caused by a large ionic radius and accessible bonding involvement of Pu III ions. Previous works demonstrated that Np V preferred to form the insertion structures more than Np VI with 18-crown-6 due to the charge shielding effect provided by the macrocycle. , Experimental data from Pu V O 2 [18-crown-6]ClO 4 revealed that a macrocycle can elongate the Pu–Pu distance, which is beneficial to weaken the Pu V disproportionation . In this case, the stabilization of Pu III within the cavity 18-crown-6 originates from electrostatic interactions as well as orbital interactions involved in the Pu III –O ligand dative bonding, as illustrated in the calculation results.…”

Section: Resultsmentioning

confidence: 95%

“…The stock solution of Pu VI O 2 (ClO 4 ) 2 was prepared according to the method in the literature . Then, an equal volume of H 2 O 2 was added to reduce Pu(VI) to Pu(IV).…”

Section: Experimental Methodsmentioning

confidence: 99%

“…Furthermore, Np VI O 2 2+ was proved to be stabilized within a functionalized crown ether . Recently, we successfully isolated a distinct pentavalent plutonium compound through reaction of Pu V O 2 + with a crown ether …”

Section: Introductionmentioning

confidence: 99%

“…10 Recently, we successfully isolated a distinct pentavalent plutonium compound through reaction of Pu V O 2 + with a crown ether. 11 We noted that all the above-mentioned studies and theoretical works are concentrated on the high-valent transuranic elements. Only a handful of thermodynamic studies associated with trivalent transuranic elements are reported.…”

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis and Characterizations of a Plutonium(III) Crown Ether Inclusion Complex

Zou

et al. 2021

Inorg. Chem.

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We report the synthesis, single-crystal structure, solid-state ultraviolet−visible−nearinfrared spectroscopy, and theoretical calculations on the first trivalent plutonium crown ether inclusion complex, [(H 3 O)(18-crown-6)][Pu(H 2 O) 4 (18-crown-6)](ClO 4 ) 4 •2(H 2 O) (denoted as Pu III -18C6). Single-crystal X-ray diffraction reveals that Pu III -18C6 crystallizes in the orthorhombic space group of Pccn, which is assembled by independent ionic pairs including [Pu(H 2 O) 4 (18-crown-6)] 3+ , [(H 3 O)(18-crown-6)] + , and perchlorate anions. The plutonium atom is fully encapsulated within the cavity of the 18-crown-6, generating a distorted bicapped square antiprism geometry. The theoretical evaluation confirms that weak Pu−O dative bond is involved between Pu III ions with 18crown-6. This work may deepen the understanding of the host−guest interactions between trivalent transuranic and macrocyclic ligands.

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Section: Resultsmentioning

confidence: 95%

“…The stock solution of Pu VI O 2 (ClO 4 ) 2 was prepared according to the method in the literature . Then, an equal volume of H 2 O 2 was added to reduce Pu(VI) to Pu(IV).…”

Section: Experimental Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis and Characterizations of a Plutonium(III) Crown Ether Inclusion Complex

Zou

et al. 2021

Inorg. Chem.

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“…[ 2 ] To date, Pu is the only element in the periodic table that was found to exist in four different oxidation states (III, IV, V, VI) simultaneously in aqueous solution. [ 3‐5 ] To effectively recover Pu from nuclear wastes and to control its fate in environment, the oxidation states of Pu must be precisely controlled. For example, in the well‐known PUREX process for nuclear spent fuel reprocessing, Pu is controlled back and forth between the IV and III oxidation states to ensure its co‐extraction with U and its subsequent separation from U.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Light‐Driven Oxidation of Pu(IV) to Pu(VI) Enables Green and Efficient Pu Recovery

et al. 2021

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Main observation and conclusion Plutonium (Pu) is a key actinide in nuclear industry and is the only element in the periodic table known to date that could exist in four different oxidation states simultaneously in aqueous solution. Efficient recovery of Pu in nuclear wastes relies greatly on the precise control of its oxidation states. Herein, we introduce a light‐driven oxidation approach that could effectively oxidize Pu(IV) to Pu(VI) in acidic solutions without the addition of extra chemical oxidants. The oxidation proceeds via the reaction of Pu(IV) with the oxidative species induced by UV light irradiation. This approach can help with the separation of Pu from other metals and can be further extended to a biphasic extraction system to achieve green and efficient stripping of Pu from an organic solvent.

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Complexes Featuring a cis‐[MUM] Core (M=Rh, Ir): A New Route to Uranium‐Metal Multiple Bonds

et al. 2023

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Although examples of multiple bonds between actinide elements and main‐group elements are quite common, studies of the multiple bonds between actinide elements and transition metals are extremely rare owing to difficulties associated with their synthesis. Here we report the first example of molecular uranium complexes featuring a cis‐[M →0false→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M] core (M=Rh, Ir), which exhibits an unprecedented arrangement of two M →0false→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U double dative bond linkages to a single U center. These complexes were prepared by the reactions of chlorine‐bridged heterometallic complexes [{U{N(CH3)(CH2CH2NPiPr2)2}(Cl)2[(μ‐Cl)M(COD)]2}] (M=Rh, Ir) with MeMgBr or MeLi, a new method for the construction of species with U−M multiple bonds. Theoretical calculations including dispersion confirmed the presence of two U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M double dative bonds in these complexes. This study not only enriches the U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M multiple bond chemistry, but also provides a new opportunity to explore the bonding of actinide elements.

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Stabilization of Plutonium(V) Within a Crown Ether Inclusion Complex

Cited by 40 publications

References 13 publications

Synthesis and Characterizations of a Plutonium(III) Crown Ether Inclusion Complex

Synthesis and Characterizations of a Plutonium(III) Crown Ether Inclusion Complex

Light‐Driven Oxidation of Pu(IV) to Pu(VI) Enables Green and Efficient Pu Recovery

Complexes Featuring a cis‐[MUM] Core (M=Rh, Ir): A New Route to Uranium‐Metal Multiple Bonds

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