[UO2Cl2(phen)2], a Simple Uranium(VI) Compound with a Significantly Bent Uranyl Unit (phen=1,10‐phenanthroline)

Schöne, S.; Radoske, Thomas; März, Juliane; Stumpf, Thorsten; Patzschke, Michael; Ikeda‐Ohno, Atsushi

doi:10.1002/chem.201703009

Cited by 22 publications

(54 citation statements)

References 48 publications

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“…Rather via a dual ligand strategy that combines coordination and supramolecular chemistry, facilitated by the flexibility of 1,10-phenanthroline molecules and stabilized via the creation of a 'π-pocket' by the 2,4,6-trihalobenzoic acid ligands, we were able to systematically explore structural aspects of uranyl bending. These findings were compared to results from density functional calculations and QTAIM analysis, which indicated that the bending of the uranyl unit has electrostatic origins and is energetically favorable until O-U-O angles reach approximately 162º, thus the uranyl bending described herein and in the recent examples from Hayton et al 37 and Ikeda-Ohno and colleagues 41 likely represent the upper limit of uranyl bending that can be achieved via coordination chemistry pathways.…”

Section: Discussionmentioning

confidence: 79%

“…A recent study from Hayton et al surveyed uranyl bending in hybrid materials and reported that the smallest observed O-U-O angles for the uranyl unit were between 166-168º. 37 In their study, they highlighted three compounds made with the uranyl cation and a 12-membered macrocycle with O-U-O angles between 161.7(5)º and 164.1(3)º, thereby setting a new mark for uranyl bending, which has recently been matched by Ikeda-Ohno et al 41 is comparable to the smallest values reported in the literature by Hayton 37 and Ikeda-Ohno, 41 and represents the most significant uranyl bending we observe in this family of complexes. Comparing the 2,4,6-trifluorobenzoic acid complexes 1 and 4, we note that complex 1 is a 'bent' 1:2 complex with respect to the uranyl cation and both ligands,…”

Section: Description Of Structuresmentioning

confidence: 86%

“…[UO2Cl2(phen)2] uranyl complex, which features two unique sets of π-interactions, one between planar phen molecules and the other between non-planar phen ligands. 41 The role of the intramolecular π-interactions in 1-3 is likely to stabilize the non-planar phen molecules, and subsequently the overall 'bent' complexes. Additional stabilization of the non-planar phen molecules is likely necessary as the U-N distances and N-U-N angles for the non-planar phen moieties in 1-3 are significantly longer and smaller (respectively) than have previously been observed in any uranyl hybrid material featuring phen.…”

Section: Description Of Structuresmentioning

confidence: 99%

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How to Bend the Uranyl Cation via Crystal Engineering

et al. 2018

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Bending the linear uranyl (UO) cation represents both a significant challenge and opportunity within the field of actinide hybrid materials. As part of related efforts to engage the nominally terminal oxo atoms of uranyl cation in noncovalent interactions, we synthesized a new uranyl complex, [UO(CHN)(CHClO)]·2HO (complex 2), that featured both deviations from equatorial planarity and uranyl linearity from simple hydrothermal conditions. Based on this complex, we developed an approach to probe the nature and origin of uranyl bending within a family of hybrid materials, which was done via the synthesis of complexes 1-3 that display significant deviations from equatorial planarity and uranyl linearity (O-U-O bond angles between 162° and 164°) featuring 2,4,6-trihalobenzoic acid ligands (where Hal = F, Cl, and Br) and 1,10-phenanthroline, along with nine additional "nonbent" hybrid materials that either coformed with the "bent" complexes (4-6) or were prepared as part of complementary efforts to understand the mechanism(s) of uranyl bending (7-12). Complexes were characterized via single crystal X-ray diffraction and Raman, infrared (IR), and luminescence spectroscopy, as well as via quantum chemical calculations and density-based quantum theory of atoms in molecules (QTAIM) analysis. Looking comprehensively, these results are compared with the small library of bent uranyl complexes in the literature, and herein we computationally demonstrate the origin of uranyl bending and delineate the energetics behind this process.

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Section: Discussionmentioning

confidence: 79%

Section: Description Of Structuresmentioning

confidence: 86%

Section: Description Of Structuresmentioning

confidence: 99%

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How to Bend the Uranyl Cation via Crystal Engineering

et al. 2018

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“…It is possible that a 7, which also features a significantly distorted Oyl-U-Oyl angle (161.8(1)°) ( Figure 3, Table 1). 57 Our X-ray crystallographic analysis of UO2(OTf)2( H N4) (6) and its analogues revealed that the uranyl-pyridinophane interaction is quite weak (as evidenced by the long U-N bond lengths). Thus, attempts to cause further perturbation of the Oyl-U-Oyl angle in uranyl will likely require a stronger interaction between the uranium center and the co-ligands.…”

Section: Steric Perturbation Of the Oyl-u-oyl Anglementioning

confidence: 88%

Understanding the origins of O_yl–U–O_ylbending in the uranyl (UO₂²⁺) ion

Hayton

2018

Dalton Trans.

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The structure of the uranyl ion (UO) has been the topic of investigation for almost a century. Since the first structural study of uranyl in 1935, over 4000 uranyl complexes have been characterized by X-ray crystallography. The vast majority of these complexes feature a linear uranyl group (e.g., O-U-O = 180°); however, there are a handful of complexes that feature much more acute O-U-O angles. In fact, the smallest experimentally observed O-U-O angles are ca. 161°. This Frontier Article catalogs every reported uranyl complex that features an O-U-O angle below 172°, and attempts to rationalize the origins of the observed O-U-O bending. In particular, I describe two distinct causes of O-U-O bending: (1) bending that occurs as a result of unfavourable steric interactions between the equatorial co-ligands and the uranyl oxo groups; and (2) bending that appears to have an electronic origin. In addition, I describe several possible avenues for future investigation. Understanding the effect that O-U-O bending has on uranyl electronic structure could ultimately provide insight into several unique aspects of the uranyl ion, such as the inverse trans influence and the involvement of the "pseudo-core" U6p orbitals in U-O bonding.

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“…To analyze the geometrica nd electronic effects more deeply when substituting py (2)w ith pic (6)o rl ut (10), quantum chemicalo ptimizations of the respective molecules were performed. All presented electronic structure calculations were done with the software packages Turbomole 7.3.1 [15] and Orca 4.2.1 [16] (for computational details please see the Computational Section).…”

Section: Structural Descriptionmentioning

confidence: 99%

Bonding Trends in Tetravalent Th–Pu Monosalen Complexes

Radoske

März

Patzschke

et al. 2020

Chemistry A European J

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The synthesis of three complex series of the form [AnCl2(salen)(Pyx)2] (H2salen=N,N′‐bis(salicylidene)ethylenediamine; Pyx=pyridine, 4‐methylpyridine, 3,5‐dimethylpyridine) with tetravalent early actinides (An=Th, U, Np, Pu) is reported with the goal to elucidate the affinity of these heavy elements for small neutral N‐donor molecules. Structure determination by single‐crystal XRD and characterization of bulk powders with infrared spectroscopy reveals isostructurality within each respective series and the same complex conformation in all reported structures. Although the trend of interatomic distances for An−Cl and An−N (imine nitrogen of salen or pyridyl nitrogen of Pyx) was found to reflect an ionic behavior, the trend of the An−O distances can only be described with additional covalent interactions for all elements heavier than thorium. All experimental results are supported by quantum chemical calculations, which confirm the mostly ionic character in the An−N and An−Cl bonds, as well as the highest degree of covalency of the An−O bonds. Structurally, the calculations indicate just minor electronic or steric effects of the additional Pyx substituents on the complex properties.

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[UO₂Cl₂(phen)₂], a Simple Uranium(VI) Compound with a Significantly Bent Uranyl Unit (phen=1,10‐phenanthroline)

Cited by 22 publications

References 48 publications

How to Bend the Uranyl Cation via Crystal Engineering

How to Bend the Uranyl Cation via Crystal Engineering

Understanding the origins of O_yl–U–O_ylbending in the uranyl (UO₂²⁺) ion

Bonding Trends in Tetravalent Th–Pu Monosalen Complexes

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[UO2Cl2(phen)2], a Simple Uranium(VI) Compound with a Significantly Bent Uranyl Unit (phen=1,10‐phenanthroline)

Cited by 22 publications

References 48 publications

How to Bend the Uranyl Cation via Crystal Engineering

How to Bend the Uranyl Cation via Crystal Engineering

Understanding the origins of Oyl–U–Oylbending in the uranyl (UO22+) ion

Bonding Trends in Tetravalent Th–Pu Monosalen Complexes

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[UO₂Cl₂(phen)₂], a Simple Uranium(VI) Compound with a Significantly Bent Uranyl Unit (phen=1,10‐phenanthroline)

Understanding the origins of O_yl–U–O_ylbending in the uranyl (UO₂²⁺) ion