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J Am Chem Soc. 2012 Jun 20;134(24):9876-8. doi: 10.1021/ja2108432. Epub 2012 Jun 12.

A direct route to bis(imido)uranium(V) halides via metathesis of uranium tetrachloride.

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1
MPA Division, Los Alamos National Laboratory, MS J514, Los Alamos, New Mexico 87545, USA.

Abstract

Metathesis reactions between uranium tetrachloride and lithium 2,6-diisopropylphenylamide in the presence of 4,4'-dialkyl-2,2'-bipyridyl (R(2)bpy; R = Me, (t)Bu) 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)(2)Cl(R(2)bpy)(2) or U(NDipp)(2)Cl(tppo)(3) (Dipp = 2,6-(i)Pr(2)C(6)H(3)). The preparation of the bromide and iodide analogues U(NDipp)(2)X(R(2)bpy)(2) was achieved by addition of CH(2)X(2) (X = Br, I) to the uranium(IV) solutions. The uranium(V) halides were characterized by X-ray crystallography and found to exhibit linear N-U-N units and short U-N bonds. Electrochemical measurements were made on the chloride bipyridine species, which reacts readily with iodine or ferrocenium to generate bis(imido)uranium(VI) cations.

PMID:
22670799
DOI:
10.1021/ja2108432
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