Abstract/Details

High valent uranium dioxo and imido complexes: Synthesis and structure


2008 2008

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Abstract (summary)

Early actinide elements have attracted considerable attention in recent years due to the need for rigorous advancements in spent nuclear fuel recycling and remediation technologies, and for their emerging versatility in organometallic chemistry. Whereas high oxidation state ions dominate environmental speciation, the corresponding high-valent organometallics are rare. These hexa- and pentavalent ions are often stabilized by the isoelectronic oxo or imido ligands, which result in robust molecular properties due to 5f/6d orbital involvement in multiple covalent bonding. The research discussed in this dissertation surveys the synthesis, isolation, and molecular and electronic structural characterization of uranyl(VI) and uranium(V)-imide complexes, and uncovers the influences imparted by a variety of functional ligand designs. In the opening report, salicylidene derived Schiff base chelates adapt to equatorial coordination and control uranyl(VI) photo- and electrochemical activity. In the second study, a ferrocenylcarboxylate ligand undergoes a transformation that renders an unprecedented bent uranyl(VI) moiety supported in a reversible coordination polymer. The final segment focuses on the rare uranium(V) oxidation state supported by pentamethylcyclopentadienyl and imido ancillary ligands in mono- and bimetallic complexes geared to elucidate the effects of ligand substitution and metal-metal communication on the 5f1 electronic configuration. Future directions and applications for each area are summarized.

Indexing (details)


Subject
Inorganic chemistry;
Nuclear chemistry
Classification
0488: Inorganic chemistry
0738: Nuclear chemistry
Identifier / keyword
Pure sciences; Actinides; Organometallics; Uranium; Uranyl complexes
Title
High valent uranium dioxo and imido complexes: Synthesis and structure
Author
Vaughn, Anthony E.
Number of pages
413
Publication year
2008
Degree date
2008
School code
0133
Source
DAI-B 70/09, Dissertation Abstracts International
Place of publication
Ann Arbor
Country of publication
United States
ISBN
9781109367355
Advisor
Duval, Paul B.
University/institution
University of Missouri - Columbia
University location
United States -- Missouri
Degree
Ph.D.
Source type
Dissertations & Theses
Language
English
Document type
Dissertation/Thesis
Dissertation/thesis number
3371103
ProQuest document ID
304518032
Copyright
Database copyright ProQuest LLC; ProQuest does not claim copyright in the individual underlying works.
Document URL
http://search.proquest.com/docview/304518032
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