Actions for Plutonium (III) and uranium (III) nitrile complexes [electronic resource].

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Plutonium (III) and uranium (III) nitrile complexes [electronic resource].

Published
Washington, D.C. : United States. Dept. of Energy, 2002.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Physical Description
16 pages : digital, PDF file
Additional Creators
Los Alamos National Laboratory, United States. Department of Energy, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
Iodine oxidation of uranium and plutonium metals in tetrahydrofuran and pyridine form AnI₃(THF)₄ and AnI₃(py)₄ (An = Pu, U). These compounds represent convenient entries Into solution An(III) chemistry in organic solvents. Extensions of the actinide metal oxidation methodology in nitrile solvents by I₂, AgPF₆, and TIPF₆ are presented here. Treatment of Pu° in acetonitrile with iodine yields a putative PuI₃(NCMe)ₓ intermediate which can be trapped with the tripodal nitrogen donor ligand tpza (tpza = (tris[(2-pyrazinyl)methyl]amine)) and forms the eight-coordinate complex (tpza)PuI₃(NCMe). Treatment of excess U° metal by iodine in acetonitrile afforded a brown crystalline mixed valence complex, [U(NCMe)₉][UI₆][I], instead of UI₃(NCMe)₄. The analogous reaction in bezonitrile forms red crystalline UI₄(NCPh)₄. In contrast, treatment of UI₃(THF)₄ with excess acetonitrile cleanly generates [U(NCMe)₉][I]₃. Oxidation of Pu° by either TI(I) or Ag(I) hexafluorophosphate salts generates a nine-coordinate homoleptic acetonitrile adduct [Pu(NCMe)₉][PF₆]₃. Attempts to oxidize U₀ with these salts were unsuccessful.
Report Numbers
E 1.99:la-ur-02-4582
la-ur-02-4582
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Note
Published through SciTech Connect.
01/01/2002.
"la-ur-02-4582"
Submitted to: Rare Earth Conference University of California, Davis, July 13-18, 2002.
Scott, B. L.; Neu, M. P.; Matonic, J. H.; Enriquez, A. E.
View MARC record | catkey: 14394041