Homoleptic Uranium(IV) Alkyl Complexes: Synthesis and Characterization

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Abstract

The addition of 4.5 equiv of LiCH(2)SiMe(3) to [Li(THF)](2)[U(O(t)Bu)(6)], in the presence of LiCl, results in the formation of the homoleptic uranium(IV) alkyl complex [Li(14)(O(t)Bu)(12)Cl][U(CH(2)SiMe(3))(5)] (1) in low yield. Complex 1 has been characterized by X-ray crystallography. As a solid, 1 is thermally stable for several days at room temperature. However, 1 rapidly decomposes in C(6)D(6), as indicated by (1)H and (7)Li{(1)H} NMR spectroscopy, owing to the lability of the [Li(14)(O(t)Bu)(12)Cl](+) cation. To avoid the formation of the [Li(14)(O(t)Bu)(12)Cl](+) counterion, alkylation of UCl(4) was investigated. Treatment of UCl(4) with 5 equiv of LiCH(2)SiMe(3) or LiCH(2)(t)Bu at -25 degrees C in THF/Et(2)O affords [Li(DME)(3)][U(CH(2)SiMe(3))(5)] (2) and [Li(THF)(4)][U(CH(2)(t)Bu)(5)] (3), respectively, in good yields. Similarly, treatment of UCl(4) with 6 equiv of MeLi or KCH(2)C(6)H(5) generates the U(IV) hexa(alkyl) complexes [Li(TMEDA)](2)[UMe(6)] (4) and {[K(THF)](3)[K(THF)(2)][U(CH(2)C(6)H(5))(6)](2)}(x) (5) in 38% and 70% yields, respectively. The structures of 3-5 have been confirmed by X-ray crystallography. Complexes 2, 3, and 5 are thermally stable solids which can be stored at room temperature for several days, whereas 4 decomposes upon warming above -25 degrees C. The electronic and magnetic properties of 2, 3, and 5 were also investigated by NIR spectroscopy and SQUID magnetometry.

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