Alexandria Digital Research Library

Manipulation of the Uranyl (UO22+) Moiety : new routes to reduction and O-U-O angle perturbation

Author:
Owens, Elizabeth Anne
Degree Grantor:
University of California, Santa Barbara. Chemistry
Degree Supervisor:
Trevor W. Hayton
Place of Publication:
[Santa Barbara, Calif.]
Publisher:
University of California, Santa Barbara
Creation Date:
2016
Issued Date:
2016
Topics:
Inorganic chemistry
Keywords:
Homoleptic
High Valent
Uranyl
Uranium
Reductive Silylation
Genres:
Dissertations, Academic and Online resources
Dissertation:
Ph.D.--University of California, Santa Barbara, 2016
Description:

The understanding of reduction and remediation of uranyl (UO22+) in the environment is a crucial consideration when planning for storage of spent nuclear fuel, as uranyl is a water-soluble environmental contaminant. This dissertation will focus on the development of new synthetic methods for the reduction of uranyl(VI) to U(IV), utilizing a synergistic relationship between a silylating reagent and a reductant. These methods provide controlled one-pot transformations at ambient temperatures and pressures, where the fates of the substituted oxo ligands have been explicitly determined.

The uranyl moiety has a strictly linear O=U=O geometry, and a cis-uranyl ion is currently unknown. Isolating a cis-uranyl complex could provide some unique insights into actinide covalency and f-orbital participation in bonding. This dissertation discuses the coordination of small macrocycles to the uranyl fragment, which generates perturbed uranyl complexes with O-U-O bond angles ranging from 168°--162°. These are some of the smallest O-U-O bond angles yet reported.

Physical Description:
1 online resource (317 pages)
Format:
Text
Collection(s):
UCSB electronic theses and dissertations
ARK:
ark:/48907/f3x92bf0
ISBN:
9781369575903
Catalog System Number:
990047512160203776
Rights:
Inc.icon only.dark In Copyright
Copyright Holder:
Elizabeth Owens
File Description
Access: Public access
Owens_ucsb_0035D_13251.pdf pdf (Portable Document Format)