Nuclear magnetic resonance study of the kinetics of ligand-exchange reactions in uranyl complexes. 5. Exchange reaction of acetylacetonate in bis(acetylacetonato)(dimethyl sulfoxide)dioxouranium(VI)

Ikeda, Yasuhisa; Tomiyasu, Hiroshi; Fukutomi, Hiroshi

doi:10.1021/ic00188a033

Cited by 17 publications

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“…1 H and 19 F NMR spectra of UO 2 (dfh) 2 DMSO and the 1 H NMR spectrum of UO 2 (acac) 2 DMSO were measured to confirm the coordination numbers of dhf, acac, and DMSO in CDCl 3 solvents. We found that the 1 H NMR spectrum of UO 2 (acac) 2 DMSO was consistent with that in a previous study, 39 and the peak area ratios of 1 H and 19 F NMR spectra of UO 2 (dfh) 2 DMSO were compatible with those predicted from the chemical structure. Accordingly, the uranyl complexes can be identified as complexes with two bidentate dhf or acac and one unidentate DMSO in the equatorial plane of the uranyl(VI) moiety.…”

Section: +supporting

confidence: 91%

“…On the basis of the above background, we previously carried out 11 B and 19 F NMR measurements of toluene solutions containing uranyl β-diketonato complexes and B(C 6 F 5 ) 2 OH because NMR spectroscopy is recognized as a helpful tool for determining the intermolecular interactions of solutes in solutions. In fact, previous NMR studies have succeeded in the characterization of structures and ligand-exchange reactions of uranyl complexes in various solvents, as well as understanding local interactions between the ligands coordinated to the uranyl moiety and solvents. − As a result, we have succeeded in discovering the possibility of LA–LB interactions between B(C 6 F 5 ) 2 OH and uranyl β-diketonato complexes . However, there are many indeterminate aspects about the LA–LB complexation mechanisms such how the LA–LB interactions change by the coordinating ligand species and solvent environments and what types of LA–LB complexes are formed.…”

Section: Introductionmentioning

confidence: 99%

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Multinuclear NMR Studies on Lewis Acid–Lewis Base Interactions between Bis(pentafluorophenyl)borinic Acid and Uranyl β-Diketonato Complexes in Toluene

2020

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In order to examine the possibility of Lewis acid–Lewis base (LA–LB) interactions between the boron atom of B(C6F5)2OH and the oxo groups (“yl” oxygen atoms) of uranyl β-diketonato complexes, we have measured the 1H, 11B, 17O, 19F NMR and IR spectra of toluene solutions containing β-diketonato complexes [UO2(acac)2DMSO or UO2(dfh)2DMSO, where acac = 2,4-pentanedionate, dfh = 1,1,1,2,2,6,6,7,7,7-decafluoroheptane-3,5-dionate, and DMSO = dimethyl sulfoxide] and B(C6F5)2OH. 11B and 17O NMR spectra of solutions containing UO2(dfh)2DMSO and B(C6F5)2OH showed no change in their chemical shifts regardless of the [B(C6F5)2OH]/[UO2(dfh)2DMSO] ratio. This indicates that there were no apparent interactions between B(C6F5)2OH and UO2(dfh)2DMSO. On the other hand, in the corresponding NMR spectra of solutions containing UO2(acac)2DMSO and B(C6F5)2OH, new signals were observed at a higher field than signals observed in the solutions containing only B(C6F5)2OH or UO2(acac)2DMSO, and their intensity changed with the [B(C6F5)2OH]/[UO2(acac)2DMSO] ratio. These results reveal that a complex with LA–LB interaction (B···OU) between the boron atom of B(C6F5)2OH and the “yl” oxygen atom of UO2(acac)2DMSO was formed. IR spectra also supported such complex formation; i.e., the asymmetric OUO stretching band of UO2(acac)2DMSO was observed to shift from 897 to 810 cm–1 with the addition of B(C6F5)2OH. Moreover, 19F NMR spectra indicated that 1:1 and 2:1 LA–LB complexes exist in equilibrium, UO{OB(C6F5)2OH}(acac)2DMSO + B(C6F5)2OH = U{OB(C6F5)2OH}2(acac)2DMSO. The thermodynamic parameters for this equilibrium were obtained as K = (2.5 ± 0.6) × 102 M–1 (at 25 °C), ΔH = −42.4 ± 5.2 kJ mol–1, and ΔS = −96.7 ± 19.4 J K–1 mol–1. In 1H NMR spectra, the signal due to −CH groups of UO2(acac)2DMSO disappeared, and three signals due to the corresponding −CH groups newly appeared with an increase in the [B(C6F5)2OH]/[UO2(acac)2DMSO] ratio. From these phenomena, it is proposed that 1:1 and 2:1 LA–LB complexes having interactions between the −CH groups of acac and the −OH group of coordinated B(C6F5)2OH are formed depending on the [B(C6F5)2OH]/[UO2(acac)2DMSO] ratio.

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Section: +supporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Multinuclear NMR Studies on Lewis Acid–Lewis Base Interactions between Bis(pentafluorophenyl)borinic Acid and Uranyl β-Diketonato Complexes in Toluene

2020

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“…The UO 2 (β-diketonato) 2 dmso and UO 2 (sap)(dmso) 2 complexes were synthesized according to the reported procedBrought to you by | New York University Bobst Library Technical Services Authenticated Download Date | 5/29/15 2:02 PM ures [15][16][17][18][19]. The UO 2 (trop) 2 dmso complex was prepared by refluxing dmso solution containing UO 2 (trop) 2 for 3 h at 80 • C. The UO 2 (trop) 2 complex was synthesized by the reported method [20].…”

Section: Methodsmentioning

confidence: 99%

Electrochemical redox reactions of uranium(VI) complexes with multidentate ligands in dimethyl sulfoxide

et al. 2005

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Uranyl complexes / Electrochemistry / Cyclic voltammetry / Redox reaction / Multidentate ligandsSummary. Electrochemical reactions of UO 2 (β-diketonato) 2 -dmso, UO 2 (trop) 2 dmso, UO 2 (sap)(dmso) 2 , and UO 2 (salen)-dmso (dmso = dimethyl sulfoxide, β-diketonate = benzoylacetonate (ba), benzoyltrifluoroacetonate (btfa), and thenoyltrifluoroacetonate (ttfa), trop = tropolonate, sap = 2-salicylidenaminophenolate, and salen = N,N -disalicylidenethylenediaminate) complexes in dmso solutions containing tetrabutylammonium perchlorate as a supporting electrolyte have been studied with cyclic voltammetry. These uranyl(VI) complexes were found to be reduced quasi-reversibly to U(V) species. The formal redox potentials (E • , vs. ferrocen/ferrocenium) for U(VI)/U(V) couples were determined to be − 1.416 V for UO 2 (ba) 2 dmso, − 1.073 V for UO 2 (btfa) 2 dmso, − 1.082 V for UO 2 (ttfa) 2 dmso, − 1.379 V for UO 2 (trop) 2 dmso, − 1.500 V for UO 2 (sap)(dmso) 2 , and − 1.602 V for UO 2 (salen)dmso. Furthermore, the resulting U(V) complexes, [UO 2 (btfa) 2 dmso] − , [UO 2 (ttfa) 2 dmso] − , and [UO 2 (salen)dmso] − , were found to be able to exist stably in dmso solutions.

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“…The UO 2 (␤-diketonate) 2 DMF and UO 2 (sap)(DMF) 2 complexes were synthesized by using the reported methods [15][16][17][18][19]. The UO 2 (trop) 2 DMF complex was prepared by refluxing UO 2 (trop) 2 in DMF at 80 • C for 3 h. The UO 2 (trop) 2 complex was synthesized by the reported method [20].…”

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Electrochemical properties of uranium(VI) complexes with multidentate ligands in N,N-dimethylformamide

Kim

Asakura

Morita

et al. 2006

Journal of Alloys and Compounds

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Nuclear magnetic resonance study of the kinetics of ligand-exchange reactions in uranyl complexes. 5. Exchange reaction of acetylacetonate in bis(acetylacetonato)(dimethyl sulfoxide)dioxouranium(VI)

Cited by 17 publications

References 0 publications

Multinuclear NMR Studies on Lewis Acid–Lewis Base Interactions between Bis(pentafluorophenyl)borinic Acid and Uranyl β-Diketonato Complexes in Toluene

Multinuclear NMR Studies on Lewis Acid–Lewis Base Interactions between Bis(pentafluorophenyl)borinic Acid and Uranyl β-Diketonato Complexes in Toluene

Electrochemical redox reactions of uranium(VI) complexes with multidentate ligands in dimethyl sulfoxide

Electrochemical properties of uranium(VI) complexes with multidentate ligands in N,N-dimethylformamide

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