Uranyl-tri- bis(silyl)amide Alkali Metal Contact and Separated Ion Pair Complexes.
Inorg Chem
; 57(11): 6571-6583, 2018 Jun 04.
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| ID: mdl-29775053
ABSTRACT
We report the preparation of a range of alkali metal uranyl(VI) tri- bis(silyl)amide complexes [{M(THF) x}{(µ-O)U(O)(Nâ³)3}] (1M) (Nâ³ = {N(SiMe3)2}-, M = Li, Na, x = 2; M = K, x = 3; M = K, Rb, Cs, x = 0) containing electrostatic alkali metal uranyl-oxo interactions. Reaction of 1M with 2,2,2-cryptand or 2 equiv of the appropriate crown ether resulted in the isolation of the separated ion pair species [U(O)2(Nâ³)3][M(2,2,2-cryptand)] (3M, M = Li-Cs) and [U(O)2(Nâ³)3][M(crown)2] (4M, M = Li, crown = 12-crown-4 ether; M = Na-Cs, crown = 15-crown-5 ether). A combination of crystallographic studies and IR, Raman and UV-vis spectroscopies has revealed that the 1M series adopts contact ion pair motifs in the solid state where the alkali metal caps one of the uranyl-oxo groups. Upon dissolution in THF solution, this contact is lost, and instead, separated ion pair motifs are observed, which is confirmed by the isolation of [U(O)2(Nâ³)3][M(THF) n] (2M) (M = Li, n = 4; M = Na, K, n = 6). The compounds have been characterized by single crystal X-ray diffraction, multinuclear NMR spectroscopy, IR, Raman, and UV-vis spectroscopies, and elemental analyses.
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MEDLINE
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En
Revista:
Inorg Chem
Año:
2018
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Article
País de afiliación:
Reino Unido