A new Pu(<scp>iii</scp>) coordination geometry in (C5H5NBr)2[PuCl3(H2O)5]·2Cl·2H2O as obtained via supramolecular assembly in aqueous, high chloride media

Surbella, Robert G.; Ducati, Lucas C.; Pellegrini, Kristi L.; McNamara, Bruce K.; Autschbach, Jochen; Schwantes, Jon M.; Cahill, Christopher L.

doi:10.1039/c7cc05988d

Cited by 10 publications

(11 citation statements)

References 41 publications

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“…The 10 coordinated oxygen atoms are provided by one 18-crown-6 ligand and four water molecules, generating a distorted bicapped square antiprism geometry (Figure S3). The Pu–O distances are in the range of 2.530(5)–2.605(5) Å, which are well in agreement with the reported bond distances for Pu III ions. − We calculated the bond valence sums (BVS) for Pu atoms in Pu III -18C6, as shown in Table S2, to be equal to 2.97, confirming the trivalent assignment of Pu Figure S4 illustrates the host–guest interactions between encapsulated atoms with 18-crwon-6 in Pu III -18C6.…”

Section: Resultssupporting

confidence: 84%

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: Resultssupporting

confidence: 84%

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

Zou

et al. 2021

Inorg. Chem.

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“…Further, consistent with this trend are observations in the solid-state structural chemistry of Pu III , which has an ionic radius (CN = 6) of 1.0 Å . Pu III –aquo–chloro complexes, including cis -Cs[Pu(H 2 O) 4 Cl 4 ], trans -Cs 5 [Pu(H 2 O) 4 Cl 4 ]Cl 4 ·2H 2 O, (Et 4 N)[Pu(H 2 O) 6 Cl 2 ]Cl 2 ·2H 2 O, and (C 5 H 5 NBr) 2 [Pu(H 2 O) 5 Cl 3 ]Cl 2 ·2H 2 O, have been reported. , …”

Section: Discussionsupporting

confidence: 71%

“…35 Further, consistent with this trend are observations in the solid-state structural chemistry of Pu III , which has an ionic radius (CN = 6) of 1.0 Å. 70 74,75 Whereas several investigations have focused on the solidstate structural chemistry of actinide(IV) chloride compounds, as highlighted above, far fewer reports have interrogated the solution-state species. In this work, we examined the correlation between the solution species and those observed in the crystalline phase using UV−vis−NIR absorption spectroscopy.…”

Section: ■ Discussionmentioning

confidence: 61%

From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry

et al. 2019

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A series of eighteen tetravalent actinide (An = Th, U, Pu) compounds were synthesized from acidic aqueous solutions containing thorium, uranium, or plutonium and a series of protonated nitrogen heterocycles. The compounds were characterized using Raman, IR, and optical absorption spectroscopies. The structures were determined using single-crystal X-ray diffraction and found to consist of [An(H 2 O) x Cl y ] 4−y (x = 4−7 and y = 2−4) or AnCl 6 2− molecular units. Breaks in the structural chemistry of the early actinides were observed, with Th adopting exclusively Th−aquo−chloro species and Pu forming only PuCl 62− ; U crystallized as both U−aquo−chloro and UCl 6 2− . The relationship between the solid-state structural units and the solution species was interrogated using UV−vis−near-IR absorption spectroscopy. A comparison of the solution and solid-state spectra suggested that, although prevalent in the solid state, particularly for U and Pu, AnCl 6 2− does not exist to an appreciable extent in the reaction solution. Despite the identification of U−aquo−chloro species in solution, there are limited reports of these complexes in the solid state. Isolation of these unique actinide(IV) chlorides as reported in this work may point to the importance of nonbonding interactions in the stabilization and precipitation of An IV structural units.

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“…The prevalence of 8–9-coordinate thorium(IV) aquohalide complexes contrasts the coordination number of the Th IV aquo ion that crystallized in the solid state as [Th(H 2 O) 10 ]·Br 4 . Related monomeric and dimeric actinide aquohalide compounds that only contain water or chloride in their first coordination sphere have also been reported; of particular note is the complex [Th(H 2 O) 7 Cl 2 ]·Cl 2 ·18-crown-6·2H 2 O, which contains a structural unit related to that observed in 8 . , Other dimeric hydrolysis products have been crystallized including [Th 2 (μ 2 -OH) 2 Cl 2 (H 2 O) 12 ]Cl 4 ·2H 2 O from acidic HCl solutions, (H 3 O) 4 [(C 2 H 5 ) 4 N] 6 [Th 2 (μ 2 -O)Cl 4 (H 2 O) 12 ] 3 [Re 4 Se 4 (CN) 12 ] 4 from acidic HCl solutions containing a rhenium cluster salt, and [Th(μ 2 -OH)Cl(H 2 O) 6 ] 2 ·Cl 4 ·18-crown-6·2H 2 O stabilized by 18-crown-6 molecules. ,, It should be noted that complete exclusion of water from the inner coordination sphere of Th is inherently difficult, consistent with the hygroscopic nature of Th salts, , yet the homoleptic ThCl 6 2– dianion has been isolated. , A similar behavior between Th IV and Pu III is noted, with monomeric plutonium(III)-aquo-chloro complexes isolated with different counterions that yielded varying aquo/chloride ratios, including cis -Cs[Pu(H 2 O) 4 Cl 4 ], trans -Cs 5 [Pu(H 2 O) 4 Cl 4 ]Cl 4 ·2H 2 O, (Et 4 N)[Pu(H 2 O) 6 Cl 2 ]Cl 2 ·2H 2 O, and (C 5 H 5 NBr) 2 [Pu(H 2 O) 5 Cl 3 ]Cl 2 ·2H 2 O in the solid state, whereas chloride was not observed to complex Pu III in aqueous solutions despite high chloride concentrations, as shown in X-ray absorption spectroscopic studies. − …”

Section: Discussionmentioning

confidence: 99%

Impact of Noncovalent Interactions on the Structural Chemistry of Thorium(IV)-Aquo-Chloro Complexes

et al. 2021

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Five novel tetravalent thorium (Th) compounds that consist of Th(H2O) x Cl y structural units were isolated from acidic aqueous solutions using a series of nitrogen-containing heterocyclic hydrogen (H) bond donors. Taken together with three previously reported phases, the compounds provide a series of monomeric ThIV complexes wherein the effects of noncovalent interactions (and H-bond donor identity) on Th structural chemistry can be examined. Seven distinct structural units of the general formulas [Th(H2O) x Cl8–x ] x−4 (x = 2, 4) and [Th(H2O) x Cl9–x ] x−5 (x = 5–7) are described. The complexes range from chloride-deficient [Th(H2O)7Cl2]2+ to chloride-rich [Th(H2O)2Cl6]2– species, and theory was used to understand the relative energies that separate complexes within this series via the stepwise chloride addition to an aquated Th cation. Electronic structure theory predicted the reaction energies of chloride addition and release of water through a series of transformations, generally highlighting an energetic driving force for chloride complexation. To probe the role of the counterion in the stabilization of these complexes, electrostatic potential (ESP) surfaces were calculated. The ESP surfaces indicated a dependence of the chloride distribution about the Th metal center on the pK a of the countercation, highlighting the directing effects of noncovalent interactions (e.g., Hbonding) on Th speciation.

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A new Pu(iii) coordination geometry in (C₅H₅NBr)₂[PuCl₃(H₂O)₅]·2Cl·2H₂O as obtained via supramolecular assembly in aqueous, high chloride media

Cited by 10 publications

References 41 publications

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

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

From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry

Impact of Noncovalent Interactions on the Structural Chemistry of Thorium(IV)-Aquo-Chloro Complexes

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A new Pu(iii) coordination geometry in (C5H5NBr)2[PuCl3(H2O)5]·2Cl·2H2O as obtained via supramolecular assembly in aqueous, high chloride media

Cited by 10 publications

References 41 publications

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

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

From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry

Impact of Noncovalent Interactions on the Structural Chemistry of Thorium(IV)-Aquo-Chloro Complexes

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Product

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A new Pu(iii) coordination geometry in (C₅H₅NBr)₂[PuCl₃(H₂O)₅]·2Cl·2H₂O as obtained via supramolecular assembly in aqueous, high chloride media