Cation−Cation Interactions between Uranyl Cations in a Polar Open-Framework Uranyl Periodate

Sullens, Tyler A.; Jensen, Rebecca A.; Shvareva, Tatiana Y.; Albrecht‐Schmitt, Thomas E.

doi:10.1021/ja031695h

Cited by 129 publications

(117 citation statements)

References 23 publications

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“…[8,14,15,30,33,[83][84][85] Recently, two T-shaped tetrameric cation-cation complexes with pentavalent [10] and hexavalent [11] uranyls have been reported. Additionally, there are some uranyl metallates with the combined Tshaped and parallel polyuranyl structures found in solidstate chemistry, [13,16] which usually exhibit one-to three-dimensional arrangements. To the best of our knowledge, there are no experimental structural reports on T-shaped and butterfly-like binuclear uranyl cation-cation complexes.…”

Section: Resultsmentioning

confidence: 99%

“…[5][6][7][8][9][10][11][12][13][14][15][16] The CCI occurs through coordination of one actinide metal center by the oxo atom of a second actinyl unit. It can lead to the formation of dimers, [4][5][6][7][8] oligomers, [9][10][11] one-dimensional chains, [12][13][14] and multi-dimensional networks [15,16] that do not necessarily require the support of ancillary ligands. The CCIs are particularly well recognized for An V (An = U, Np and Pu) [4-6, 10, 12, 17-20] and have recently been identified in U VI chemistry.…”

Section: Introductionmentioning

confidence: 99%

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Binuclear Uranium(VI) Complexes with a “Pacman” Expanded Porphyrin: Computational Evidence for Highly Unusual Bis‐Actinyl Structures

Pan

Shamov

Schreckenbach

2010

Chemistry A European J

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On the basis of uranyl complexes reacting with a polypyrrolic ligand (H(4)L), we explored structures and reaction energies of a series of new binuclear uranium(VI) complexes using relativistic density functional theory. Full geometry optimizations on [(UO(2))(2)(L)], in which two uranyl groups were initially placed into the pacman ligand cavity, led to two minimum-energy structures. These complexes with cation-cation interactions (CCI) exhibit unusual coordination modes of uranyls: one is a T-shaped (T) skeleton formed by two linear uranyls {O(exo)=U(2)=O(endo)-->U(1)(=O(exo))(2)}, and another is a butterfly-like (B) unit with one linear uranyl coordinating side-by-side to a second cis-uranyl. The CCI in T was confirmed by the calculated longest distance and lowest stretching vibrational frequency of U(2)=O(endo) among the four U=O bonds. Isomer B is more stable than T, for which experimental tetrameric analogues are known. The formation of B and T complexes from the mononuclear [(UO(2))(H(2)L)(thf)] (M) was found to be endothermic. The further protonation and dehydration of B and T are thermodynamically favorable. As a possible product, we have found a trianglelike binuclear uranium(VI) complex having a O=U=O=U=O unit.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Binuclear Uranium(VI) Complexes with a “Pacman” Expanded Porphyrin: Computational Evidence for Highly Unusual Bis‐Actinyl Structures

Pan

Shamov

Schreckenbach

2010

Chemistry A European J

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“…Very similar values of the U VI =O distances were found in extended frameworks that contain UO 2 2+ ···UO 2 2+ cation-cation interactions. [25,26] The replacement of one UO 2 + ion by a UO 2 2+ ion results in significant differences in the metric parameters of the tetranuclear core, which is less distorted in 6 than in 4. The bond valence sum analysis, performed using the empirical expression and constants proposed by Brown and Altermatt, [27] is in agreement with the presence of three pentavalent uranium ions and one localized hexavalent uranium ion in 6 (see the Supporting Information).…”

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confidence: 99%

Stable Pentavalent Uranyl Species and Selective Assembly of a Polymetallic Mixed‐Valent Uranyl Complex by Cation–Cation Interactions

et al. 2009

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Cation-cation interactions are a key feature of actinide chemistry. These interactions can be used in two areas that currently attract great interest, namely the expansion of felement supramolecular chemistry and the enhancement of magnetic interactions in actinide compounds. [1][2][3][4][5][6][7][8][9][10][11][12] Moreover, oligomeric cation-cation species that present mutually coordinated actinyl ions are likely to play a crucial role in nuclear waste reprocessing and in the migration of radioactive actinides in the environment. [1] Cation-cation interactions are known to be important in neptunyl(V) structural chemistry, [13] but are more rarely found in uranyl(VI) compounds because of the lower basicity of the UO 2 2+ oxygen atoms. Dimeric compounds formed through the mutual binding of pentavalent uranyl(V) ions have been proposed as intermediates in the disproportionation of pentavalent uranyl ions to UO 2 2+ and U IV species.[14]As a result, bulky ligands have been used in the past few years to disfavor cation-cation interactions and allow the synthesis of rare UO 2 + complexes, [15][16][17][18][19][20][21] which have been the subject of two recent reviews.[ [8] The presence of antiferromagnetic coupling between the oxo-bridged uranium centers was unambiguously demonstrated for the dimetallic complex but is less evident for the tetrametallic complex. [8] The decomposition of these polymetallic complexes of pentavalent uranyl ions to UO 2 2+ and U IV species starts rapidly after dissolution in organic solvents and is accelerated by traces of water. From these reactivity studies, it occurred to us that the stability of these polymeric systems could possibly be modulated by fine-tuning the electronic and steric properties of the ligand and coordinating cation. Herein, we report the first example of a UO 2 + ···UO 2 + complex that is highly stable in organic solvents and, significantly, is stable toward hydrolysis. We also describe the selective synthesis and the structure of the first mixed-valent UO 2 + ···UO 2 2+ molecular complex, which provides a rare example of functionalization of the U VI =O group. [20,22] By breaking away from the current trend of using steric bulk to prevent dimer formation and the associated disproportionation of UO 2 + complexes, we show that the non-bulky Schiff base ligand salen 2À (N,N'-bis(salicylidene)ethylenediamine) can stabilize pentavalent uranyl ions through the formation of a highly stable cation-cation complex. Moreover, we demonstrate that the resulting tetrameric uranyl(V) complex exhibits unambiguous antiferromagnetic coupling between the uranium centers.The reaction of the recently reported UO 2 + complex [(UO 2 Py 5 )(KI 2 Py 2 )] n (2; Py = pyridine) [23] with salenK 2 in pyridine led to the formation of the complex of pentavalent uranyl 3 as a violet powder that was insoluble in pyridine. The elemental analysis of 3 indicates the presence of a complex of general formula [(UO 2 )(salen)K(Py)]·1.4 KI, which most likely has a solid-state polymeric structure. Compound ...

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“…We cannot ignore the importance of research on behavior of this metal in biosystems. A score of publications have been surfaced on the complexation tendencies of uranium(VI) with different biological ligands [3,4]. The aim of this work is to examine the interaction of uranium, in its (IV) oxidation state, with a ligand of biological significance i.e.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Spectral and Electrochemical Studies of Complex of Uranium(IV) with Pyridine-3-Carboxylic Acid

Nazir¹,

Naqvi²

2013

AJAC

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The investigation of complexation of uranium with biological active ligands is vital for understanding uranium speciation in biosystems. A number of studies have been undertaken for investigating the complexation of uranium in its (VI) oxidation states but similar investigations pertaining to the interaction of uranium, in lower oxidation states, with biological ligands is scarce. The aim of the work is to bridge this gap and studies have been carried out to determine the coordination pattern of pyridine-3-carboxylic acid with uranium(IV). Semi-micro analysis, spectro-analytical techniques, magnetic susceptibility and cyclic voltammetry have been employed for the characterization of the synthesized complex.

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Cation−Cation Interactions between Uranyl Cations in a Polar Open-Framework Uranyl Periodate

Cited by 129 publications

References 23 publications

Binuclear Uranium(VI) Complexes with a “Pacman” Expanded Porphyrin: Computational Evidence for Highly Unusual Bis‐Actinyl Structures

Binuclear Uranium(VI) Complexes with a “Pacman” Expanded Porphyrin: Computational Evidence for Highly Unusual Bis‐Actinyl Structures

Stable Pentavalent Uranyl Species and Selective Assembly of a Polymetallic Mixed‐Valent Uranyl Complex by Cation–Cation Interactions

Synthesis, Spectral and Electrochemical Studies of Complex of Uranium(IV) with Pyridine-3-Carboxylic Acid

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