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Issue 29, 2010
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Uranium(iv) amide and halide derivatives of two tripodal tris(N-arylamido-dimethylsilyl)methanes

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Abstract

Reaction of three equivalents of ArNH2 (Ar = 3,5-Me2C6H3) with HC(SiMe2Br)3 in the presence of the auxiliary base NEt3 afforded the tripodal tris(N-arylamine-dimethylsilyl)methane HC{SiMe2N(H)Ar}3 (1) in 83% yield. Three-fold deprotonation of 1 with n-butyllithium afforded the corresponding tri-lithium tris(N-arylamido-dimethylsilyl)methane etherate [HC{SiMe2N(Li)Ar}3(OEt2)] (2) in 92% yield. Salt elimination reactions between 2 or the known complex [HC{SiMe2N(Li)Ar′}3(OEt2)2] (3) (Ar′ = 4-MeC6H4) with one equivalent of uranium(IV) tetrachloride afforded the corresponding tris(N-arylamido-dimethylsilyl)methane uranium(IV) chloride complexes as monomeric [U(Cl){HC(SiMe2NAr)3}(THF)] (4) and dinuclear [{HC(SiMe2NAr′)3}U(Cl)(μ-Cl)U(THF)2{(Ar′NSiMe2)3CH}] (5) species in 70 and 90% crystalline yields, respectively. Treatment of 4 and 5 with one equivalent of trimethylsilyl iodide resulted in halide exchange and formation of [U(I){HC(SiMe2NAr)3}(THF)2] (6) and [U(I){HC(SiMe2NAr′)3}(THF)] (7) in 85 and 90% yields, respectively. The heteroleptic amide [U(NCy2){HC(SiMe2NAr)3}(THF)] (8) was prepared from the reaction between 4 and one equivalent of lithium dicyclohexylamide and was isolated in 78% yield. Analogous attempts to prepare [U(NCy2){HC(SiMe2NAr′)3}(THF)] (9) from 5 consistently resulted in intractable mixtures of products. Complexes 1–8 have been characterised by X-ray crystallography, NMR spectroscopy, FTIR spectroscopy, room temperature Evans method solution magnetic moments, and CHN micro-analyses.

Graphical abstract: Uranium(iv) amide and halide derivatives of two tripodal tris(N-arylamido-dimethylsilyl)methanes

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Article information


Submitted
09 Dec 2009
Accepted
02 Feb 2010
First published
12 Mar 2010

Dalton Trans., 2010,39, 6638-6647
Article type
Paper

Uranium(IV) amide and halide derivatives of two tripodal tris(N-arylamido-dimethylsilyl)methanes

D. Patel, W. Lewis, A. J. Blake and S. T. Liddle, Dalton Trans., 2010, 39, 6638
DOI: 10.1039/B926018H

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