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Probing the chemistry, electronic structure and redox energetics in pentavalent organometallic actinide complexes [electronic resource].

Published
Washington, D.C. : United States. Dept. of Energy, 2008.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
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
Complexes of the early actinides (Th-Pu) have gained considerable prominence in organometallic chemistry as they have been shown to undergo chemistries not observed with their transition- or lanthanide metal counterparts. Further, while bonding in f-element complexes has historically been considered to be ionic, the issue of covalence remains a subject of debate in the area of actinide science, and studies aimed at elucidating key bonding interactions with 5f-orbitals continue to garner attention. Towards this end, our interests have focused on the role that metal oxidation state plays in the structure, reactivity and spectral properties of organouranium complexes. We report our progress in the synthesis of substituted U{sup V}-imido complexes using various routes: (1) Direct oxidation of U{sup IV}-imido complexes with copper(I) salts; (2) Salt metathesis with U{sup V}-imido halides; (3) Protonolysis and insertion of an U{sup V}-imido alkyl or aryl complex with H-N{double_bond}CPh₂ or N{triple_bond}C-Ph, respectively, to form a U{sup V}-imido ketimide complex. Further, we report and compare the crystallographic, electrochemical, spectroscopic and magnetic characterization of the pentavalent uranium (C₅Me₅)₂U({double_bond}N-Ar)(Y) series (Y = OTf, SPh, C{triple_bond}C-Ph, NPh₂, OPh, N{double_bond}CPh₂) to further interrogate the molecular, electronic, and magnetic structures of this new class of uranium complexes.
Report Numbers
E 1.99:la-ur-08-05056
E 1.99: la-ur-08-5056
la-ur-08-5056
la-ur-08-05056
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Note
Published through SciTech Connect.
01/01/2008.
"la-ur-08-05056"
" la-ur-08-5056"
Inorganic Chemistry ISSN 0020-1669; INOCAJ FT
Graves, Christopher R; Kiplinger, Jaqueline L; Morris, David E; Vaughn, Anthony E.
Funding Information
AC52-06NA25396
View MARC record | catkey: 14393158