Simple Preparations of the Anhydrous and Solvent-Free Uranyl and Cerium(IV) Triflates UO2(OTf)2 and Ce(OTf)4 − Crystal Structures of UO2(OTf)2(py)3 and [{UO2(py)4}2(μ-O)][OTf]2

Berthet, Jean‐Claude; Lance, M.; Nierlich, Martine; Ephritikhine, Michel

doi:10.1002/1099-0682(200009)2000:9<1969::aid-ejic1969>3.0.co;2-0

Cited by 65 publications

(20 citation statements)

References 25 publications

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“…Chloroform-d and pyridine-d 5 were purchased from Cambridge Isotope Laboratories, dried with molecular sieves, and degassed by three freeze−pump−thaw cycles. 4,6-Di-tert-butyl-2-[(2,6-diisopropylphenyl)imino]quinone ( dipp iq), 23 potassium graphite (KC 8 ), 26 uranyl dichloride ([UO 2 Cl 2 (THF) 2 ] 2 ), 27 uranyl triflate UO 2 (OTf) 2 (THF) 3 , 28 and uranium tetrachloride (UCl 4 ) 29 were prepared according to literature procedures. 18-Crown-6 (18-C-6) and B-chlorocatecholborane (Cl-BCat) were purchased from Sigma-Aldrich and dried under vacuum on a Schlenk line overnight prior to use.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O–C Bonds via Acylation

et al. 2018

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A series of uranyl compounds with the redoxactive iminoquinone ligand have been synthesized, and their electronic structures elucidated using multinuclear NMR, EPR, electronic absorption spectroscopies, SQUID magnetometry, and X-ray crystallography. Characterization and analysis of the iminoquinone (iq 0 ) complex, ( dipp iq)UO 2 (OTf) 2 THF (1-iq), the iminosemiquinone (isq 1− ) complex, ( dipp isq) 2 UO 2 THF (2i s q ) , a n d t h e a m i d o p h e n o l a t e ( a p 2 − ) complex, [( dipp ap) 2 UO 2 THF][K(18-crown-6)(THF) 2 ] 2 (3-ap crown) show that reduction events are ligand-based, with the uranium center remaining in the hexavalent state. Reactivity of 2-isq with B-chlorocatecholborane or pivaloyl chloride leads to U−O uranyl bond scission and reduction of U(VI) to U(IV) concomitant with ligand oxidation along with organic byproducts. 18 O isotopic labeling experiments along with IR spectroscopy, mass spectrometry, and multinuclear NMR spectroscopy confirm that the organic byproducts contain oxygen atoms which originate from U−O uranyl bond activation.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O–C Bonds via Acylation

et al. 2018

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“…The uranyl salt used to prepare the solutions in both ionic liquids was [UO 2 ][OTf] 2 , synthesized according to the procedure described in ref . The chloride ions were added to the uranyl(VI) solution as [Bmim]Cl and [MeBu 3 N]Cl respectively in [Bmim][Tf 2 N] (H 2 O: 125 ± 20 ppm) and [MeBu 3 N][Tf 2 N] (H 2 O: 175 ± 30 ppm).…”

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Uranyl Complexation by Chloride Ions. Formation of a Tetrachlorouranium(VI) Complex in Room Temperature Ionic Liquids [Bmim][Tf₂N] and [MeBu₃N][Tf₂N]

et al. 2006

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The tetrachlorouranium(VI) complex is formed in [Bmim][Tf2N] and [MeBu3N][Tf2N] from a uranium(VI) solution in the presence of a stoichiometric quantity of chloride ions. The [UVIO2Cl4]2- absorption and emission spectra show bands splitting in comparison with the [UVIO2]2+ spectra, as observed in the solid state, organic solvents, and chloroaluminate-based ionic liquids. The fluorescence lifetime of [UO2Cl4]2- in [MeBu3N][Tf2N] is 0.7 +/- 0.1 mus. The reduction potential of this complex is -1.44 and -1.8 V vs Ag/Ag+ respectively in [Bmim][Tf2N] and [MeBu3N][Tf2N] and does not depend on the chloride concentration. The mechanism proposed for the redox process is a monoelectronic reduction to form [UVO2Cl4]3-, followed by a chemical reaction. The tetrachlorouranium(V) complex seems more stable in [Bmim][Tf2N] than in [MeBu3N][Tf2N]. The electrochemical analysis put in evidence specific interactions of the ionic liquid cation with the uranium anionic species.

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“…Transition-metal and lanthanide triflate complexes and their respective chemistry have been known for some time, and in recent years these compounds have enjoyed considerable utility as Lewis acid catalysts in organic chemistry, as important precursors in inorganic chemistry, and as building blocks in supramolecular chemistry . In contrast, molecules possessing actinide−triflate bonds are quite scarce and until recently have been limited to a handful of thorium(IV) and uranyl (UO 2 2+ ) triflate complexes. The paucity of available starting materials has clearly hampered the development of chemistry involving organoactinide triflate complexes.…”

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[(C₅Me₅)₂U(Me)(OTf)]₂: A New Reagent for Uranium Metallocene Chemistry. Preparation of the First Actinide Hydrazonato Complexes

et al. 2002

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The synthesis and characterization of the first actinide hydrazonato complex, (C5Me5)2U(η2(N,N‘)-CH3NNCPh2)(OTf) (3), has been made possible by use of the organouranium(IV) trifluoromethanesulfonate (triflate) complex [(C5Me5)2U(CH3)(OTf)]2 (2; OTf = OSO2CF3), which is derived from the reaction between (C5Me5)2U(CH3)2 and Ph3COTf. The related chemistry for (C5Me5)2U(CH3)(Cl) is also reported. All new complexes have been structurally characterized.

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Simple Preparations of the Anhydrous and Solvent-Free Uranyl and Cerium(IV) Triflates UO2(OTf)2 and Ce(OTf)4 − Crystal Structures of UO2(OTf)2(py)3 and [{UO2(py)4}2(μ-O)][OTf]2

Cited by 65 publications

References 25 publications

Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O–C Bonds via Acylation

Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O–C Bonds via Acylation

Uranyl Complexation by Chloride Ions. Formation of a Tetrachlorouranium(VI) Complex in Room Temperature Ionic Liquids [Bmim][Tf₂N] and [MeBu₃N][Tf₂N]

[(C₅Me₅)₂U(Me)(OTf)]₂: A New Reagent for Uranium Metallocene Chemistry. Preparation of the First Actinide Hydrazonato Complexes

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Simple Preparations of the Anhydrous and Solvent-Free Uranyl and Cerium(IV) Triflates UO2(OTf)2 and Ce(OTf)4 − Crystal Structures of UO2(OTf)2(py)3 and [{UO2(py)4}2(μ-O)][OTf]2

Cited by 65 publications

References 25 publications

Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O–C Bonds via Acylation

Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O–C Bonds via Acylation

Uranyl Complexation by Chloride Ions. Formation of a Tetrachlorouranium(VI) Complex in Room Temperature Ionic Liquids [Bmim][Tf2N] and [MeBu3N][Tf2N]

[(C5Me5)2U(Me)(OTf)]2: A New Reagent for Uranium Metallocene Chemistry. Preparation of the First Actinide Hydrazonato Complexes

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Uranyl Complexation by Chloride Ions. Formation of a Tetrachlorouranium(VI) Complex in Room Temperature Ionic Liquids [Bmim][Tf₂N] and [MeBu₃N][Tf₂N]

[(C₅Me₅)₂U(Me)(OTf)]₂: A New Reagent for Uranium Metallocene Chemistry. Preparation of the First Actinide Hydrazonato Complexes