Manipulation of the Uranyl (UO22+) Moiety : new routes to reduction and O-U-O angle perturbation
- 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:
- Reductive Silylation,
Uranium,
High Valent,
Uranyl, and
Homoleptic - Genres:
- Online resources and Dissertations, Academic
- 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
- Other Versions:
- http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqm&rft_dat=xri:pqdiss:10194598
- ARK:
- ark:/48907/f3x92bf0
- ISBN:
- 9781369575903
- Catalog System Number:
- 990047512160203776
- Copyright:
- Elizabeth Owens, 2016
- Rights:
- In Copyright
- Copyright Holder:
- Elizabeth Owens
File | Description |
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Access: Public access | |
Owens_ucsb_0035D_13251.pdf | pdf (Portable Document Format) |