1,4,7,10-Tetraoxacyclododecane-uranyl nitrate dihydrate

Armagˇan, N.

doi:10.1107/s0567740877008206

Cited by 14 publications

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“…Studies have also demonstrated that the trans -dioxo actinyl-type species of U(VI), − Np(V), , and Pu(V) can be chelated by 18-crown-6 derivatives in the solid state (see Chart ). Virtually nothing is known, however, regarding the properties of crown-chelated uranyl complexes in solution, a situation attributable to the apparent propensity of actinyl ions to be lost from simple 18-crown-6 derivatives in the presence of coordinating solvents such as water or dimethyl sulfoxide. ,, These findings have been thought to be in accord with the observation that the majority of related solid-state structures reveal actinide centers with water ligands in the first coordination sphere that hydrogen-bond to crown ethers held in the secondary sphere . Additionally, although crown ethers and cryptands are ubiquitous in actinide organometallic chemistry, when they are utilized, they typically encapsulate countercations like Na + or K + that charge balance anionic actinide species. , …”

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confidence: 99%

Synthesis, Isolation, and Study of Heterobimetallic Uranyl Crown Ether Complexes

Golwankar,

Ervin,

Makoś

et al. 2024

J. Am. Chem. Soc.

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Although crown ethers can selectively bind many metal cations, little is known regarding the solution properties of crown ether complexes of the uranyl dication, UO 2 2+ . Here, the synthesis and characterization of isolable complexes in which the uranyl dication is bound in an 18-crown-6-like moiety are reported. A tailored macrocyclic ligand, templated with a Pt(II) center, captures UO 2 2+ in the crown moiety, as demonstrated by results from single-crystal X-ray diffraction analysis. The U(V) oxidation state becomes accessible at a quite positive potential (E 1/2 ) of −0.18 V vs Fc +/0 upon complexation, representing the most positive U VI /U V potential yet reported for the UO 2 n+ core. Isolation and characterization of the U(V) form of the crown complex are also reported here; there are no prior reports of reduced uranyl crown ether complexes, but U(V) is clearly stabilized by crown chelation. Joint computational studies show that the electronic structure of the U(V) form results in significant weakening of U−O oxo bonding despite the quite positive reduction potential at which this species can be accessed, underscoring that crown-ligated uranyl species could demonstrate unique reactivity under only modestly reducing conditions.

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