Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C5Me5)2U(μ-H)]2

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• 作者：Justin K. Pagano ; Jacquelyn M. Dorhout ; Kenneth R. Czerwinski ; David E. Morris ; Brian L. Scott ; Rory Waterman ; Jaqueline L. Kiplinger
• 刊名：Organometallics
• 出版年：2016
• 出版时间：March 14, 2016
• 年：2016
• 卷：35
• 期：5
• 页码：617-620
• 全文大小：290K
• ISSN：1520-6041

文摘

This work demonstrates that the oxidation state and chemistry of uranium hydrides can be tuned with temperature and the stoichiometry of phenylsilane. The trivalent uranium hydride [(C₅Me₅)₂U–H]_x (5) was found to be comprised of an equilibrium mixture of U(III) hydrides in solution at ambient temperature. A single U(III) species can be selectively prepared by treating (C₅Me₅)₂UMe₂ (4) with 2 equiv of phenylsilane at 50 °C. The U(III) system is a potent reducing agent and displayed chemistry distinct from the U(IV) system [(C₅Me₅)₂U(H)(μ-H)]₂ (2), which was harnessed to prepare a variety of organometallic complexes, including (C₅Me₅)₂U(dmpe)(H) (6), and the novel uranium(IV) metallacyclopentadiene complex (C₅Me₅)₂U(C₄Me₄) (11).