Dissertation
THE STABILIZATION OF LOW-VALENT URANIUM COMPLEXES FEATURING BULKY TERPHENYL AMIDO LIGANDS
Doctor of Philosophy (PhD), Washington State University
2026
Abstract
The trialkyl terphenyl amide ligand system [R3TerNH]– ([R3TerNH]– = 2,6-(2,4,6-R3C6H2)2C6H3NH–; R = Me, Et, iPr) has proven to be a powerful, tunable scaffold to stabilize U(II) and U(III) complexes, and the research described in this work highlights the impact of this system in studying low-valent uranium species. The steric effects of the substituted terphenyl amide ligand system were investigated to determine the required steric bulk to isolate a neutral U(II) complex. The triisopropyl- (previously reported) and triethyl-substituted ligand were able to stabilize a neutral U(II) complexes (R3TerNH)2U (R = Et, iPr); however, the trimethyl-substituted system yielded a bimetallic "triple-decker" sandwich complex with a doubly reduced terphenyl arenide ligand bridging two U(III) metal centers. The reduction chemistry of the neutral U(II) species was explored through the oxidative addition of diphenyl dichalcogenides (PhEEPh; E = S, Se, Te) to generate U(IV) bis-(terphenyl amido) bis-(phenyl chalcogenolate) complexes where changes in coordination geometry and complex stability were observed. This library of uranium chalcogenolate species also allows for investigation into the metal-ligand covalency down the chalcogen series. The versatility of the terphenyl amide ligand was further explored in the mixed ligand system Cp*(R3TerNH)UI (R = Me, Et, iPr) where it was determined these species feature a highly functionalizable iodide position. This group can be substituted for [BH4]–, –Me, –Bu, –Bz, –SPh, a bipyridyl organic radical to give rare examples of U(III)–ligand interactions.
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Details
- Title
- THE STABILIZATION OF LOW-VALENT URANIUM COMPLEXES FEATURING BULKY TERPHENYL AMIDO LIGANDS
- Creators
- Vincent M Groner
- Contributors
- James M Boncella (Advisor)Xiaofeng Guo (Committee Member)Ivan Popov (Committee Member)Qiang Zhang (Committee Member)
- Awarding Institution
- Washington State University
- Academic Unit
- Department of Chemistry
- Theses and Dissertations
- Doctor of Philosophy (PhD), Washington State University
- Number of pages
- 396
- Identifiers
- 99901393804801842
- Language
- English
- Resource Type
- Dissertation