Probing the chemistry, electronic structure and redox energetics in pentavalent organometallic actinide complexes

• Published in: Inorganic chemistry
• Main Authors: Graves, Christopher R, Vaughn, Anthony E, Morris, David E, Kiplinger, Jaqueline L
• Format: Journal Article
• Language: English
• Published: United States 01.01.2008
• Subjects: ACTINIDE COMPLEXES; ACTINIDES; BONDING; CHEMISTRY; COMPLEXES; COPPER; COVALENCE; ELECTRONIC STRUCTURE; HALIDES; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; INTERACTIONS; METALS; ORGANOMETALLIC COMPOUNDS; OXIDATION; PLUTONIUM; RARE EARTHS; REACTIVITY; SALTS; SYNTHESIS; THORIUM; URANIUM; URANIUM COMPLEXES; VALENCE
• ISSN: 0020-1669; 1520-510X

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}CPh{sub 2} 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 (C{sub 5}Me{sub 5}){sub 2}U({double_bond}N-Ar)(Y) series (Y = OTf, SPh, C{triple_bond}C-Ph, NPh{sub 2}, OPh, N{double_bond}CPh{sub 2}) to further interrogate the molecular, electronic, and magnetic structures of this new class of uranium complexes.