Oxidative ammonolysis of uranium(IV) fluorides to uranium(VI) nitride

Yeamans, C. B.; Silva, Chinthaka M.; Cerefice, Gary; Czerwinski, Kenneth R.; Hartmann, Thomas; Burrell, Anthony K.; Sattelberger, Alfred P.

doi:10.1016/j.jnucmat.2007.06.022

Cited by 34 publications

(30 citation statements)

References 21 publications

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“…In our own studies of the reactions of UF 6 and UF 4 with liquid ammonia, we obtained signal-green trisammonium monoammine heptafluorouranate(IV) ammonia, [ (2) as the products in almost quantitative yields and were thus able to finally clarify the course of the reactions of these uranium fluorides with liquid ammonia. To the best of our knowledge, these compounds represent the first characterized ammonia complexes of uranium fluorides.…”

Section: Resultsmentioning

confidence: 99%

“…Only through a determination of their compositions and structures has the elucidation of the reactions of liquid ammonia with UF 6 and UF 4 finally been made possible. Compounds 1 and 2 have been characterized by single-crystal structure analysis at low temperature because neither is stable under ambient conditions.…”

Section: Discussionmentioning

confidence: 99%

“…It is a key compound in the synthesis of uranium hexaA C H T U N G T R E N N U N G fluoride, UF 6 , which is used to enrich the fissile 235 U isotope and is finally converted to the nuclear fuel UO 2 . Uranium nitride, UN, is expected to be superior to the conventional UO 2 [1][2][3][4] in many of its properties and is seen as a promising nuclear fuel for fourth-generation nuclear reactors.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, a multi-step synthesis of UN from UO 2 and NH 4 HF 2 was recently proposed. [6,7] Another route to highly pure uranium nitride may lie in the usage of molecular uranium nitrides or azides as the starting materials. [8][9][10][11] Obviously, a more direct pathway towards uranium nitrides could be by reactions between UF 6 and NH 3 .…”

Section: Introductionmentioning

confidence: 99%

“…[8][9][10][11] Obviously, a more direct pathway towards uranium nitrides could be by reactions between UF 6 and NH 3 . Studies of the reaction of UF 6 with NH 3 were first reported 51 years ago, [12,13] and the products were assumed to be UF 5 and NH 4 UF 5 based on observation of their colors and elemental analysis data. Burk and Berthold tried to elucidate the nature of the reactions of green salt with ammonia at various temperatures and arrived at the conclusion that UF 4 is insoluble in liquid ammonia.…”

Section: Introductionmentioning

confidence: 99%

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UF₆ and UF₄ in Liquid Ammonia: [UF₇(NH₃)]³⁻ and [UF₄(NH₃)₄]

Kraus

Baer

2009

Chemistry A European J

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From the reaction of uranium hexafluoride UF6 with dry liquid ammonia, the [UF7(NH3)]3- anion and the [UF4(NH3)4] molecule were isolated and identified for the first time. They are found in signal-green crystals of trisammonium monoammine heptafluorouranate(IV) ammonia (1:1; [NH4]3[UF7(NH3)].NH3) and emerald-green crystals of tetraammine tetrafluorouranium(IV) ammonia (1:1; [UF4(NH3)4].NH3). [NH4]3[UF7(NH3)].NH3 features discrete [UF7(NH3)]3- anions with a coordination geometry similar to a bicapped trigonal prism, hitherto unknown for U(IV) compounds. The emerald-green [UF4(NH3)4].NH3 contains discrete tetraammine tetrafluorouranium(IV) [UF4(NH3)4] molecules. [UF4(NH3)4].NH3 is not stable at room temperature and forms pastel-green [UF4(NH3)4] as a powder that is surprisingly stable up to 147 degrees C. The compounds are the first structurally characterized ammonia complexes of uranium fluorides.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

UF₆ and UF₄ in Liquid Ammonia: [UF₇(NH₃)]³⁻ and [UF₄(NH₃)₄]

Kraus

Baer

2009

Chemistry A European J

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Activation of Small Molecules by Molecular Uranium Complexes

Pierre¹,

Meyer²

2014

Progress in Inorganic Chemistry

126

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Synthesis of Thorium(IV) and Uranium(IV) Salicylaldiminate Pseudo‐Halide Complexes

et al. 2015

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To explore the coordination chemistry of salicylaldiminate ligands as a non‐cyclopentadienyl ligand framework, we report the synthesis of their ThIV and UIV complexes. Deprotonation of (NC5H4)N=C(H)(3,5‐tBu2C6H2)OH (1), (NC9H6)N=C(H)(3,5‐tBu2C6H2)OH (2), and (CH3SC6H4)N=C(H)(3,5‐tBu2C6H2)OH (3) with sodium hydride and the subsequent addition of 0.5 equivalents of [UI4(1,4‐dioxane)2] yielded [{(NC5H4)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2UI2] (4), [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2UI2] (5), and [{(CH3SC6H4)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,S)}2UI2] (6), respectively. The reaction of 3 equivalents of the sodium salt of 1 afforded [{(NC5H4)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}3U]I3 (7). By using [ThCl4(dme)2], [{(NC5H4)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2ThCl2] (8) and [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2ThCl2] (9) were isolated. The metathesis of both chloride ligands in 9 with NaN3 led to a rare thorium azide product, [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2Th(N3)2] (10). The reaction of 5 with AgOTf (OTf = O3SCF3) afforded [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2U(OTf)2] (11), and the subsequent reaction of 11 with 2 equivalents of NaN3 provided [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2U(N3)2] (12). The reaction of 5 with 2 equivalents of AgNO3 produced [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2U{NO3‐κ2(O,O)}2] (13). Each complex was characterized by 1H NMR and IR spectroscopy and, with the exception of 11, their structures were determined by X‐ray crystallographic analysis.

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Oxidative ammonolysis of uranium(IV) fluorides to uranium(VI) nitride

Cited by 34 publications

References 21 publications

UF₆ and UF₄ in Liquid Ammonia: [UF₇(NH₃)]³⁻ and [UF₄(NH₃)₄]

UF₆ and UF₄ in Liquid Ammonia: [UF₇(NH₃)]³⁻ and [UF₄(NH₃)₄]

Activation of Small Molecules by Molecular Uranium Complexes

Synthesis of Thorium(IV) and Uranium(IV) Salicylaldiminate Pseudo‐Halide Complexes

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Oxidative ammonolysis of uranium(IV) fluorides to uranium(VI) nitride

Cited by 34 publications

References 21 publications

UF6 and UF4 in Liquid Ammonia: [UF7(NH3)]3− and [UF4(NH3)4]

UF6 and UF4 in Liquid Ammonia: [UF7(NH3)]3− and [UF4(NH3)4]

Activation of Small Molecules by Molecular Uranium Complexes

Synthesis of Thorium(IV) and Uranium(IV) Salicylaldiminate Pseudo‐Halide Complexes

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Product

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UF₆ and UF₄ in Liquid Ammonia: [UF₇(NH₃)]³⁻ and [UF₄(NH₃)₄]

UF₆ and UF₄ in Liquid Ammonia: [UF₇(NH₃)]³⁻ and [UF₄(NH₃)₄]