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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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posted on 18.02.2016, 00:00 by Justin K. Pagano, Jacquelyn M. Dorhout, Kenneth R. Czerwinski, David E. Morris, Brian L. Scott, Rory Waterman, Jaqueline L. Kiplinger
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).