Cerium(III) and Uranium(IV) Complexes of the 2-Fluorophenyl Trimethylsilyl Amide Ligand: C–F → Ln/An Interactions that Modulate the Coordination Spheres of f-Block Elements

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• 作者：Haolin Yin ; Patrick J. Carroll ; Eric J. Schelter
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 6, 2016
• 年：2016
• 卷：55
• 期：11
• 页码：5684-5692
• 全文大小：519K
• 年卷期：0
• ISSN：1520-510X

文摘

2-fluorophenyl trimethylsilyl amide, N(SiMe₃)(C₆H₄F)⁻ was shown to engage in stronger C–F → Ce^III interactions than pentafluorophenyl trimethylsilyl amide, N(SiMe₃)(C₆F₅)⁻, through a comparative study of the Ce^III model complexes Ce[N(SiMe₃)(C₆H₄F)]₃ (1-F₁) and Ce[N(SiMe₃)(C₆F₅)]₃ (1-F₅). The presence of multiple C–F → U^IV interactions led to complexes 2-X (X = Cl, C≡CPh, OMe) with threefold geometries, featuring a trigonal pyramidal UN₃Cl core in the solid-state structures. Density functional theory calculations were applied to 2-Cl to investigate the strength of the C–F → U^IV interactions and the influence of such interactions on resulting geometries.