Polynuclear uranium(IV) compounds with (μ3-oxo)U3 or (μ4-oxo)U4 cores and compartmental Schiff base ligands

Salmon, Lionel; Thuéry, Pierre; Ephritikhine, Michel

doi:10.1016/j.poly.2005.10.015

Cited by 30 publications

(25 citation statements)

References 41 publications

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“… Illustration of the U IV ‐oxo bridged tetranuclear cores observed in the solid state including (a) [U 4 O 4 ] 8+ , (b) [U 4 O 2 ] 12+ , and (c) [U 4 O] 14+ . The tetramer isolated in this work adopts the motif shown in (b).…”

Section: Resultsmentioning

confidence: 98%

“…The majority of these tetramers were stabilized by bulky ligands, with μ 2 /μ 3 ‐nitrogen atoms bridging the metal centers . Only eight of the reported tetramers contained μ 2 /μ 3 /μ 4 ‐oxo groups and were found to adopt one of three unique structural units as shown in Figure . The tetranuclear core observed in 2 (Figure b) is the most common of the tetramers with five other compounds adopting related structural units.…”

Section: Resultsmentioning

confidence: 99%

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Mononuclear to Polynuclear U^IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

Vanagas

Higgins

Wacker

et al. 2020

Chemistry A European J

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Uranium(IV)c omplexation by 2-furoic acid (2-FA) was examined to better understand the effects of ligand identity and reactionc onditions on speciesf ormationa nd stability.F ive compounds were isolated:[ UCl 2 (2-FA) 2 (H 2 O) 2 ] n (1), [U 4 Cl 10 O 2 (THF) 6 (2-FA) 2 ]·2THF (2), [U 6 O 4 (OH) 4 (H 2 O) 3 (2-FA) 12 ]·7THF·H 2 O( 3), [U 6 O 4 (OH) 4 (H 2 O) 2 (2-FA) 12 ]·8.76 H 2 O( 4), and [U 38 Cl 42 O 54 (OH) 2 (H 2 O) 20 ]·m H 2 O·n THF (5). The structures were determinedb ys ingle-crystal X-ray diffractiona nd further characterized by Raman, IR, and optical absorption spectroscopy.T he thermals tability and magnetic behavior of the compounds werealso examined. Variationsinthe synthetic conditions led to notable differences in the structural units observed in the solids tate. At low H 2 O/THF ratios, a tetranuclear oxo-bridged [U 4 O 2 ]c ore was isolated.A ging of this solution resulted in the formationaU 38 oxo cluster capped by chloro and water ligands. However,a ti ncreasing water concentrationso nly hexanuclear units wereo bserved. In all cases, at temperatures of 100-120 8C, UO 2 nanoparticles formed.[a] Dr.Supporting information (Structure refinement details;Thermal ellipsoid plots;B ond Valence Summation values;P owderX -ray diffractionpatterns; UV/Vis-NIR spectra;Raman and IR spectra;TGA spectra;M agnetic data; TEM data)a nd the ORCID identification number(s) for the author(s) of this articlecan be foundu nder: https://doi.Figure 5. Binding modes of the 2-FAu nits observed in 3 (a,c,d) and 4 (b-d).

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Mononuclear to Polynuclear U^IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

Vanagas

Higgins

Wacker

et al. 2020

Chemistry A European J

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“…In addition to the practical concerns, uranium compounds are of interest due to electrochemical properties [8][9][10][11][12][13] as well as due to supramolecular aspects [32][33][34][35][36][37][38][39] involving uranyl oxygens of the linear uranyl dication, UO 2 2+ , as a supramolecular building unit [13,14]. Salmon et al have reported a number of mono-, tri-, tetra-, and hexanuclear uranium(IV) complexes derived from compartmental Schiff base ligands obtained on condensation of salicylaldehyde or substituted salicylaldehydes with diamines [15][16][17]. We have previously reported a dialkoxo-bridged diuranyl(VI) compound, [(UO 2 ) 2 (L) 2 (dmf) 2 ] derived from a Schiff base tridentate ligand (H 2 L = obtained on condensation of 3-methoxysalicylaldehyde and 2-aminoethanol) [13].…”

Section: Introductionmentioning

confidence: 99%

Syntheses, structures, and electrochemistry of a dinuclear compound and a mononuclear–mononuclear cocrystalline compound of uranyl(VI)

Fleck¹,

Hazra

Majumder

et al. 2008

Cryst. Res. Technol.

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Syntheses, structures, and electrochemistry of a dialkoxo-bridged diuranyl(VI) compound(1) and a mononuclear-mononuclear cocrystalline compound , two dimethylformamide (dmf) molecules and two UO 2 2+ centers. Three C-H⋅⋅⋅O type hydrogen bonds involving one uranyl oxygen, two dmf hydrogens, and the imine hydrogen link the dinuclear units into a two-dimensional network. Compound 2 is a cocrystal of two mononuclear units,. In unit 1, the non-coordinated water molecule forms hydrogen bonds with oxygens of phenoxo, ethoxy, and coordinated water molecules resulting in the formation of an inclusion product. The overall supramolecular structure of compound 2 is onedimensional and consists of interlinked self-assembled dimeric unit of unit 1 and unit 2. Cyclic voltammetric measurements reveal that the uranium (VI) quasireversibly at E ½ = -773 mV with ΔE P = 121 mV, while the metal center in2) is reduced reversibly with E ½ = -765 mV with ΔE P = 68 mV.Dedicated to Prof. Ladislav Bohatý on the occasion of his 60 th birthday

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“…The pbp U IV centers in the triangular trianion of 56 are held together by one µ 3 -oxido group, while all the chlorido ligands are terminal. The tetra-anionic Schiff base bridges the three metal ions in a 3.221111 mode ( Figure 19) [113]. The four U IV centers in the dication of 56 are in a distorted tetrahedral topology bridged by the µ 4 -oxido group.…”

Section: Dinuclear and Oligonuclear Uranyl(v) Complexesmentioning

confidence: 99%

“…The two crystallographically independent metal ions are in different environments; one is 8-coordinate with a dodecahedral geometry and the other is 9-coordinate in a capped square antiprismatic coordination environment. The U IV ions are held together through two 3.221111 (L 32 ) 4− and two 2.211100 (H 2 L 32 ) 2− ligands [113]. The (L 32 ) 4− Schiff-base ligand in the tetranuclear cation does not match exactly the usual boat (umbrella) or stepped conformations, while the (H 2 L 32 ) 2− ligand is a borderline case of the umbrella shape in which the two aromatic rings of each dianion are facing each other (with a dihedral angle of ≈25 • ).…”

Section: Dinuclear and Oligonuclear Uranyl(v) Complexesmentioning

confidence: 99%

Oligonuclear Actinoid Complexes with Schiff Bases as Ligands—Older Achievements and Recent Progress

Tsantis

Tzimopoulos

Hołyńska

et al. 2020

IJMS

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Even 155 years after their first synthesis, Schiff bases continue to surprise inorganic chemists. Schiff-base ligands have played a major role in the development of modern coordination chemistry because of their relevance to a number of interdisciplinary research fields. The chemistry, properties and applications of transition metal and lanthanoid complexes with Schiff-base ligands are now quite mature. On the contrary, the coordination chemistry of Schiff bases with actinoid (5f-metal) ions is an emerging area, and impressive research discoveries have appeared in the last 10 years or so. The chemistry of actinoid ions continues to attract the intense interest of many inorganic groups around the world. Important scientific challenges are the understanding the basic chemistry associated with handling and recycling of nuclear materials; investigating the redox properties of these elements and the formation of complexes with unusual metal oxidation states; discovering materials for the recovery of trans-{UVIO2}2+ from the oceans; elucidating and manipulating actinoid-element multiple bonds; discovering methods to carry out multi-electron reactions; and improving the 5f-metal ions’ potential for activation of small molecules. The study of 5f-metal complexes with Schiff-base ligands is a currently “hot” topic for a variety of reasons, including issues of synthetic inorganic chemistry, metalosupramolecular chemistry, homogeneous catalysis, separation strategies for nuclear fuel processing and nuclear waste management, bioinorganic and environmental chemistry, materials chemistry and theoretical chemistry. This almost-comprehensive review, covers aspects of synthetic chemistry, reactivity and the properties of dinuclear and oligonuclear actinoid complexes based on Schiff-base ligands. Our work focuses on the significant advances that have occurred since 2000, with special attention on recent developments. The review is divided into eight sections (chapters). After an introductory section describing the organization of the scientific information, Sections 2 and 3 deal with general information about Schiff bases and their coordination chemistry, and the chemistry of actinoids, respectively. Section 4 highlights the relevance of Schiff bases to actinoid chemistry. Sections 5–7 are the “main menu” of the scientific meal of this review. The discussion is arranged according the actinoid (only for Np, Th and U are Schiff-base complexes known). Sections 5 and 7 are further arranged into parts according to the oxidation states of Np and U, respectively, because the coordination chemistry of these metals is very much dependent on their oxidation state. In Section 8, some concluding comments are presented and a brief prognosis for the future is attempted.

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Polynuclear uranium(IV) compounds with (μ3-oxo)U3 or (μ4-oxo)U4 cores and compartmental Schiff base ligands

Cited by 30 publications

References 41 publications

Mononuclear to Polynuclear U^IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

Mononuclear to Polynuclear U^IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

Syntheses, structures, and electrochemistry of a dinuclear compound and a mononuclear–mononuclear cocrystalline compound of uranyl(VI)

Oligonuclear Actinoid Complexes with Schiff Bases as Ligands—Older Achievements and Recent Progress

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Polynuclear uranium(IV) compounds with (μ3-oxo)U3 or (μ4-oxo)U4 cores and compartmental Schiff base ligands

Cited by 30 publications

References 41 publications

Mononuclear to Polynuclear UIV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

Mononuclear to Polynuclear UIV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

Syntheses, structures, and electrochemistry of a dinuclear compound and a mononuclear–mononuclear cocrystalline compound of uranyl(VI)

Oligonuclear Actinoid Complexes with Schiff Bases as Ligands—Older Achievements and Recent Progress

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Mononuclear to Polynuclear U^IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

Mononuclear to Polynuclear U^IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation