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Updated: Jun 10, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Uranium(IV) amide and halide derivatives of two tripodal tris(N-arylamido-dimethylsilyl)methanes
Dipti Patel1, William Lewis, Alexander J Blake
1School of Chemistry, University of Nottingham, University Park, Nottingham, UK NG7 2RD.
Abstract:
Reaction of three equivalents of ArNH(2) (Ar = 3,5-Me(2)C(6)H(3)) with HC(SiMe(2)Br)(3) in the presence of the auxiliary base NEt(3) afforded the tripodal tris(N-arylamine-dimethylsilyl)methane HC{SiMe(2)N(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{SiMe(2)N(Li)Ar}(3)(OEt(2))] (2) in 92% yield. Salt elimination reactions between 2 or the known complex [HC{SiMe(2)N(Li)Ar'}(3)(OEt(2))(2)] (3) (Ar' = 4-MeC(6)H(4)) with one equivalent of uranium(IV) tetrachloride afforded the corresponding tris(N-arylamido-dimethylsilyl)methane uranium(IV) chloride complexes as monomeric [U(Cl){HC(SiMe(2)NAr)(3)}(THF)] (4) and dinuclear [{HC(SiMe(2)NAr')(3)}U(Cl)(mu-Cl)U(THF)(2){(Ar'NSiMe(2))(3)CH}] (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(SiMe(2)NAr)(3)}(THF)(2)] (6) and [U(I){HC(SiMe(2)NAr')(3)}(THF)] (7) in 85 and 90% yields, respectively. The heteroleptic amide [U(NCy(2)){HC(SiMe(2)NAr)(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(NCy(2)){HC(SiMe(2)NAr')(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.
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