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Title: Uranyl(V) and (VI) complexes featuring bulky silylamide ligands
Author: Moulding, David
ISNI:       0000 0004 8504 8045
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2019
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The fundamental chemistry of uranium is severely lacking, in spite of its wide spread use within the nuclear industry. A key area of focus is that of uranyl {UVIO2}2+; a linear dioxo cation which is the most common form of uranium observed, and its uranyl(V) counterpart {UVO2}+. The study of {UVO2}+ is hindered by its predisposition to easily decompose via disproportionation. This has important implications, as it is a perceived intermediate within environmental reactions and therefore could hold valuable information with regards to nuclear waste management. Herein, work using mono-ionic, monodentate silylamide with uranyl(VI) and (V) is discussed. Chapter One is an introduction to the literature regarding uranium and uranyl, with a key focus on uranyl(V) and organometallic uranyl(VI) chemistry. Chapter Two is an investigation into a uranyl tris-amide complex, featuring a variety of different alkali metal counter-ion and coordination environments. It was found that the solution state properties of all complexes remain constant, with variations in the solid state observed depending whether a sequestering agent was used. Chapter Three discussed the extension of the uranyl bis-silylamide family. The subsequent impact on uranyl moiety was measured using a variety of different spectroscopic techniques and was determined to be minimal. This potentially indicates that the inability to coordinate larger silylamides is a result of steric, rather than electronic factors. Chapter Four consists of work that primarily looks at the reduction chemistry of the complexes isolated in Chapters Two and Three. The resulting products are characterised and their origins are discussed. Additionally, attempts to expand on the uranyl bis-silylamides (Chapter Two) by preparing the equivalent uranyl tris-silylamides complexes is also discussed. Chapter Five is discussion of a new protocol for cyclopentadienyl inclusion onto a uranyl moiety. The limitations of this new protocol with regards to cyclopentadienyl substitution and preparation methods are discussed. Chapter Six follows on from Chapter Five with the investigation of additional parameters. The cross over point between mono and bis Cp substitution on the uranyl silylamides (Chapter Three) are investigated and discussed.
Supervisor: Natrajan, Louise ; Mills, David Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Inorganic ; Silylamide ; Uranyl ; Uranium ; Coordination ; Chemistry ; Organometallic