Crystal structure of two new molecular adducts of uranyl nitrate with 2,2′-6,2″-terpyridine

Чарушникова, И. А.; Auwer, Christophe Den

doi:10.1134/s1070328407010083

Cited by 24 publications

(31 citation statements)

References 8 publications

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“…For the complexes reported in the experiments, a parallel structure of two uranyl ions connected by oxygen bridges in polynuclear complexes is the most common. [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.…”

Section: Resultsmentioning

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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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%

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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“…In our recent study of uranyl complexes with monodentate first row ligands, 20 we found evidence to support this weakening as being due to covalent interactions in the equatorial plane causing a reduction of the covalent component of the U-O yl interaction, with the weakening of the U-O yl bond proportional to the degree of equatorial electron sharing. Moving from simple mono-to bi-and tridentate ligands, uranyl has been observed to form complexes with, for example, bipyridine and various derivatives, 21,22 with some species demonstrating interesting luminescent properties, 23 and the terpyridine ligand has been observed to coordinate uranyl 21,22 as well as U(III), 24 acting to bind the latter selectively over the trivalent lanthanides. UO 2 Cl 2 -3(THF) reacts with another tridentate ligand, 2,6-bis(2-benzimidazolyl)pyridine (H 2 BBP) to produce three complexes: 25 [(UO 2 )(H 2 BBP)Cl 2 ], [(UO 2 )(HBBP)(Py)Cl], and [(UO 2 )(BBP)(Py) 2 ], with the effects on the uranyl dication in terms of U-O yl bond lengthening and deviation of the uranyl unit from linearity found to increase with shorter U-N bonds and increased planarity of the BBP ligand.…”

Section: Introductionmentioning

confidence: 99%

Assessing covalency in equatorial U–N bonds: density based measures of bonding in BTP and isoamethyrin complexes of uranyl

Pietro

Kerridge

2016

Phys. Chem. Chem. Phys.

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Calculations performed at the density functional level of theory have been used to investigate complexes of uranyl with the expanded porphyrin isoamethyrin and the bis-triazinyl-pyridine (BTP) ligands, the latter of which is well-known to be effective in the separation of trivalent lanthanides and actinides. Analysis has been performed using a range of density-based techniques, including the Quantum Theory of Atoms in Molecules (QTAIM), the Electron Localisation Function (ELF) and the reduced density gradient (RDG). The effects of peripheral alkyl substituents on UO2-isoamethyrin, known to be vital for proper replication of the experimental geometry, are considered. Evidence for comparable amounts of covalent character has been found in the largely ionic U-N bonds of UO2-isoamethyrin and [UO2(BTP)2](2+) and examination of the variation in the electronic characteristics of the uranyl unit upon complexation in both of these cases reveal striking similarities in the nature of the U-N bonding and the effect of this bonding on the U-Oyl interaction, as well as evidence of donation into the U-N bonding region from the uranyl unit itself.

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“…The resulting coordination polyhedron UO 8 adopts a hexagonal bipyramidal geometry with the uranyl oxygen atoms in apical positions. Two nitrates (and two L ligands) are transsituated to each other with respect to the UO 2 U species as it was previously observed in complexes with a similar [{UO 2 (NO 3 )X} 2 (μ 2 -O 2 )] composition, where X is the bidentate chelate neutral ligand (X = tetraethylsuccinamide, 16 2,2′-bipyridyl 17 or 5,5′-dimethyl-2,2′-bipyridine 18 ). The severe disorder of the peroxo, NO 3 and uranyl groups in 2 provides no possibility to analyze its molecular geometry in detail, but the mutual disposition of the constituting moieties can still be assessed.…”

Section: Synthesis and Solid State Characterization Of The Complexesmentioning

confidence: 56%

Extraction and coordination studies of a carbonyl–phosphine oxide scorpionate ligand with uranyl and lanthanide(iii) nitrates: structural, spectroscopic and DFT characterization of the complexes

et al. 2016

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Hybrid scorpionate ligand (OPPh2)2CHCH2C(O)Me (L) was synthesized and characterized by spectroscopic methods and X-ray diffraction. The selected coordination chemistry of L with UO2(NO3)2 and Ln(NO3)3 (Ln = La, Nd, Lu) has been evaluated. The isolated mono- and binuclear complexes, namely, [UO2(NO3)2L] (1), [{UO2(NO3)L}2(μ2-O2)]·EtOH (2), [La(NO3)3L2]·2.33MeCN (3), [Nd(NO3)3L2]·3MeCN (4), [Nd(NO3)2L2]+·(NO3)−·EtOH (5) and [Lu(NO3)3L2] (6) have been characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray structures have been determined for complexes 1-5. Intramolecular intraligand π-stacking interactions between two phenyl fragments of the coordinated ligand(s) were observed in all complexes 1-5. The π-stacking interaction energy was estimated from Bader's AIM theory calculations performed at the DFT level. Solution properties have been examined using IR and multinuclear ((1)H, (13)C, and (31)P) NMR spectroscopy in CD3CN and CDCl3. Coordination modes of L vary with the coordination polyhedron of the metal and solvent nature showing many coordination modes: P(O),P(O), P(O),P(O),C(O), P(O),C(O), and P(O). Preliminary extraction studies of U(VI) and Ln(III) (Ln = La, Nd, Ho, Yb) from 3.75 M HNO3 into CHCl3 show that scorpionate L extracts f-block elements (especially uranium) better than its unmodified prototype (OPPh2)2CH2.

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Crystal structure of two new molecular adducts of uranyl nitrate with 2,2′-6,2″-terpyridine

Cited by 24 publications

References 8 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

Assessing covalency in equatorial U–N bonds: density based measures of bonding in BTP and isoamethyrin complexes of uranyl

Extraction and coordination studies of a carbonyl–phosphine oxide scorpionate ligand with uranyl and lanthanide(iii) nitrates: structural, spectroscopic and DFT characterization of the complexes

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