Extending Stannyl Anion Chemistry to the Actinides: Synthesis and Characterization of a Uranium–Tin Bond

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• 作者：Matthew S. Winston ; Enrique R. Batista ; Ping Yang ; Aaron M. Tondreau ; James M. Boncella
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 6, 2016
• 年：2016
• 卷：55
• 期：11
• 页码：5534-5539
• 全文大小：369K
• 年卷期：0
• ISSN：1520-510X

文摘

We have synthesized a rare example of a uranium(IV) stannyl (κ⁴-N(CH₂CH₂NSi(ⁱPr)₃)₃U(SnMe₃), 1) via transmetalation with LiSnMe₃. This complex has been characterized crystallographically and shown to have a U–Sn bond length of 3.3130(3) Å, substantially longer than the only other crystallographically observed U–Sn bond (3.166 Å). Computational studies suggest that the U–Sn bond in 1 is highly polarized, with significant charge transfer to the stannylate ligand. We briefly discuss plausible mechanistic scenarios for the formation of 1, which may be relevant to other transmetalation processes involving heavy main group atoms. Furthermore, we demonstrate the reducing ability of [SnMe₃]⁻ in the absence of strongly donating ligands on U(IV).