A Direct Route to Bis(imido)uranium(V) Halides via Metathesis of Uranium Tetrachloride

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• 作者：Robert E. Jilek ; Liam P. Spencer ; Richard A. Lewis ; Brian L. Scott ; Trevor W. Hayton ; James M. Boncella
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：June 20, 2012
• 年：2012
• 卷：134
• 期：24
• 页码：9876-9878
• 全文大小：204K
• 年卷期：v.134,no.24(June 20, 2012)
• ISSN：1520-5126

文摘

Metathesis reactions between uranium tetrachloride and lithium 2,6-diisopropylphenylamide in the presence of 4,4鈥?dialkyl-2,2鈥?bipyridyl (R₂bpy; R = Me, ^tBu) or triphenylphosphine oxide (tppo) appear to generate bis(imido)uranium(IV) in situ. These extremely reactive complexes abstract chloride from dichloromethane to generate U(NDipp)₂Cl(R₂bpy)₂ or U(NDipp)₂Cl(tppo)₃ (Dipp = 2,6-ⁱPr₂C₆H₃). The preparation of the bromide and iodide analogues U(NDipp)₂X(R₂bpy)₂ was achieved by addition of CH₂X₂ (X = Br, I) to the uranium(IV) solutions. The uranium(V) halides were characterized by X-ray crystallography and found to exhibit linear N鈥揢鈥揘 units and short U鈥揘 bonds. Electrochemical measurements were made on the chloride bipyridine species, which reacts readily with iodine or ferrocenium to generate bis(imido)uranium(VI) cations.