Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et)

Lichtscheidl, Alejandro G.; Pagano, Justin K.; Scott, Brian L.; Nelson, Andrew T.; Kiplinger, Jaqueline L.

doi:10.3390/inorganics4010001

Cited by 8 publications

(13 citation statements)

References 88 publications

(109 reference statements)

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“…To understand the generality of this fluorination method, the reactivity of Me 3 SnF with tetravalent uranium metallocene and non‐metallocene ligand frameworks was tested. Reaction of Me 3 SnF with the uranium(IV) aryloxide–chloride complex, (C 5 Me 5 ) 2 U(Cl)(O‐2,6‐ i Pr 2 C 6 H 3 ) ( 5 ), proceeds smoothly at room temperature to afford Me 3 SnCl and the corresponding uranium(IV) fluoride complex (C 5 Me 5 ) 2 U(F)(O‐2,6‐ i Pr 2 C 6 H 3 ) ( 6 ) in 93 % yield [Equation (2)]. Likewise, treatment of the uranium(IV) tris(aryloxide) iodide and tris(amide) chloride complexes, U(I)(O‐2,6‐ t Bu 2 C 6 H 3 ) 3 ( 7 ) and U(Cl)[N(SiMe 3 ) 2 ] 3 ( 9 ), with Me 3 SnF forms U(F)(O‐2,6‐ t Bu 2 C 6 H 3 ) 3 ( 8 ) and U(F)[N(SiMe 3 ) 2 ] 3 ( 10 ) in 53 % and 93 % yields, respectively [Equations (3) and (4)].…”

Section: Resultsmentioning

confidence: 99%

“…As shown in Equation (6), similar chemistry was observed for uranium. Reaction of the uranium(IV) dichloride and dibromide complexes (C 5 Me 5 ) 2 UX 2 [X = Cl ( 13 ), Br ( 14 )] in the presence of phosphine oxides afforded the monometallic difluoride uranium(IV) complexes (C 5 Me 5 ) 2 UF 2 (O=PR 3 ) [R = CH 3 ( 15 , 97–99 %); R = Ph ( 16 , 70–99 %); R = Cy ( 17 , 71–77 %)]. Due to the basicity of the fluoride ligand, a characteristic feature of organometallic fluoride complexes is the tendency to form fluoride bridges between two or more metal atoms.…”

Section: Resultsmentioning

confidence: 99%

“…All solvents (Aldrich) were purchased anhydrous, dried with KH for 48 h, passed through a column of activated alumina, and stored over activated 3 Å molecular sieves prior to use. (C 5 Me 5 ) 2 U(X)(=N‐2,6‐ i Pr 2 C 6 H 3 ) (X = Cl, Br, I),[9a], [9b] (C 5 Me 5 ) 2 U(Cl)(O‐2,6‐ i Pr 2 C 6 H 3 ), U(I)(O‐2,6‐ t Bu 2 C 6 H 3 ) 3 , U(Cl)[N(SiMe 3 ) 2 ], (C 5 Me 5 ) 2 UCl 2 , (C 5 Me 5 ) 2 UBr 2 , (1,2,4‐ t Bu 3 C 5 H 2 ) 2 ThCl 2 , and Me 3 SnF were prepared according to literature procedures.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

et al. 2017

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

et al. 2017

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“…This increase in bond distance is consistent with literature trends among other uranium-halide compounds. 150,169,173,175,176 Another important feature of these compounds to note is that the bipyridine-like structure is no longer reduced (as it is for (C5Me5)2U(2,2'-bpy) 165 ) in all but the fluorine compound. This can be seen through the bond length of the 2,2' bond between pyridine rings.…”

Section: Crystal Structuresmentioning

confidence: 99%

Synthesis of Actinide Materials for the Study of Basic Actinide Science and Rapid Separation of Fission Products

Dorhout

2017

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This dissertation covers several distinct projects relating to the fields of nuclear forensics and basic actinide science. Post-detonation nuclear forensics, in particular, the study of fission products resulting from a nuclear device to determine device attributes and information, often depends on the comparison of fission products to a library of known ratios. The expansion of this library is imperative as technology advances. Rapid separation of fission products from a target material, without the need to dissolve the target, is an important technique to develop to improve the library and provide a means to develop samples and standards for testing separations. Several materials were studied as a proof-of-concept that fission products can be extracted from a solid target, including microparticulate (< 10 µm diameter) dUO2, porous metal organic frameworks (MOFs) synthesized from depleted uranium (dU), and other organicbased frameworks containing dU. The targets were irradiated with fast neutrons from one of two different neutron sources, contacted with dilute acids to facilitate the separation of fission products, and analyzed via gamma spectroscopy for separation yields. The results indicate that smaller particle sizes of dUO2 in contact with the secondary matrix KBr yield higher separation yields than particles without a secondary matrix. It was also discovered that using 0.1 M HNO3 as a contact acid leads to the dissolution of the target material. Lower concentrations of acid were used for future experiments. In the case of the MOFs, a larger pore size in the framework leads to higher separation yields when contacted with 0.01 M HNO3. Different types of frameworks also yield different results. The second portion of this dissertation describes efforts to better understand electronic structure and bonding of the actinide metals in various environments. One project involved studying thorium and uranium bonding with the soft-donor chalcogenides, specifically sulfur. Results from these studies include the synthesis and characterization of the novel (C5Me5)2Th(SMe)2 complex; the synthesis of (C5Me5)2ThS5 by myriad routes, indicating the product is a thermodynamic sink; and evidence that sulfur is inserted iv into the thorium-carbon bond of (C5Me5)2ThMe2 to form the pentasulfide. The second project involved unique activation of the strong carbon-halide bonds present in benzyl-halides mediated by a uranium-(2,2'-bipyridine) complex. The resultant products include a series of uranium-halide bonds from fluoride to iodide, and the addition of the benzyl group to the bipyridine ring. Studies of the mechanism indicate that the benzyl group is added first to the 6 position of the ring before migrating to its final place at the 4 position. The final project utilized a novel gold-tetrazolate complex that can be tailored to add highnitrogen ligands to actinides in a facile and safe way. This transfer ligand was used to synthesize new uranium-tetrazolate species. A brief exploration into using the transfer ligand to add tetra...

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“…As with the d-block, organometallic lanthanide chemistry has proven to be of vital use in the development of homogeneous catalysis. This issue reflects this growing interest with papers demonstrating the synthesis of organometallic lanthanide complexes using imide (Anwander and co-workers) [15], amidinate (Edelman and co-workers) [16], reduced bipyridine (Mills and co-workers) [17] and metallocene (Ce 4+ complexes by Gordon and co-workers [18], the reactivity of Sm 2+ by Maron and co-workers [19] and U 3+ /U 4+ bromides by Kiplinger and co-workers [20]) ligand frameworks. A review from Eisen and co-workers [21] is devoted to actinide catalysis and an article from Visseaux and co-workers [22] details the extension of organometallic Nd catalysis into the solid state demonstrating the numerous current applications of these interesting species.…”

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confidence: 99%

Rare Earth and Actinide Complexes

Mansell

Liddle

2016

Inorganics

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The rare earth metals (scandium, yttrium, lanthanum and the subsequent 4f elements) and actinides (actinium and the 5f elements) are vital components of our technology-dominated society. Examples include the fluorescent-red europium ions used in euro banknotes to deter counterfeiting [1], the radioactive americium used in smoke detectors [2] that save countless lives every year as well as neodymium used in the strongest permanent magnets [3]. However, the rare earth and actinide elements remain poorly recognised by non-scientists, and even by many undergraduates in chemistry.The similar radii of the respective +3 cations (Figure 1) belies their individually unique spectral [4] and magnetic [5] properties that contribute to their fascinating chemistry. In this Special Issue, devoted to molecular rare earth and actinide complexes, work from Natrajan and co-workers [6] has explored how fluorinated ligands improve the luminescence of 4f complexes, while Baker and co-workers [7] investigated the optical properties, as well as structure, of a new class of uranyl selenocyanate. Pointillart and co-workers' article [8] bridges the areas of lanthanide optical and magnetic properties-literally-by using bridging tetrathiafulvalene derivatives. The growing field of Single Molecule Magnetism originates in the d-block, but recent interest in the f-elements has been growing. Powell and co-workers [9] explore the use of dimeric dysprosium (which has a highly anisotropic f-electron distribution) compounds with a "hula-hoop" geometry, defined by the ligand that sits in an equatorial plane around both Dy atoms. The main current medical use for the lanthanides, as Magnetic Resonance Imaging (MRI) contrast agents, also relies on the unique electronic properties of the lanthanides. The article by Parac-Vogt and co-workers [10] demonstrates the combination of gadolinium for MRI imaging (thanks to its seven unpaired electrons) connected to a luminescent BODIPY fragment in order to explore combined MRI and optical imaging, addressing the drawbacks of both techniques through their complementary properties. The rare earth metals (scandium, yttrium, lanthanum and the subsequent 4f elements) and actinides (actinium and the 5f elements) are vital components of our technology-dominated society. Examples include the fluorescent-red europium ions used in euro banknotes to deter counterfeiting [1], the radioactive americium used in smoke detectors [2] that save countless lives every year as well as neodymium used in the strongest permanent magnets [3]. However, the rare earth and actinide elements remain poorly recognised by non-scientists, and even by many undergraduates in chemistry.The similar radii of the respective +3 cations (Figure 1) belies their individually unique spectral [4] and magnetic [5] properties that contribute to their fascinating chemistry. In this Special Issue, devoted to molecular rare earth and actinide complexes, work from Natrajan and co-workers [6] has explored how fluorinated ligands improve the luminescence of 4f com...

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Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et)

Cited by 8 publications

References 88 publications

Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

Synthesis of Actinide Materials for the Study of Basic Actinide Science and Rapid Separation of Fission Products

Rare Earth and Actinide Complexes

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