Physical Sciences and Mathematics Commons^™

Electrochemical And Corrosion Examination Of Copper Under Deep Geologic Conditions For The Application Of Nuclear Waste Containers, Taylor L. Martino

Electronic Thesis and Dissertation Repository

Copper is the selected material for the fabrication of nuclear fuel waste containers in Sweden, Finland and Canada due to its corrosion resistance in the anoxic aqueous environments, anticipated in deep geological repositories. A potential oxidant for copper is bisulphide produced either by the dissolution of minerals or by sulphate-reducing bacteria. The primary goals of this thesis were to determine the mechanism of corrosion of copper in bisulphide environments and to investigate the chemistry of the bentonite porewater that will ultimately be in contact with the copper container.

The mechanism of sulphide film growth and the details of copper corrosion …

Exploring The Synthesis, Structure, And Reactivity Of Phosphorus-Chalcogen Heterocycles, Cameron Graham

Electronic Thesis and Dissertation Repository

In recent years, the field of low-coordinate main group chemistry has seen significant research interest due to their unique structures and unprecedented reactivity. Conversely, the area of phosphinidene chalcogenides, a low-coordinate phosphorus and chalcogen species, have yet to be thoroughly explored. In this context, this dissertation describes the synthesis of a number of phosphorus-chalcogen heterocycles that can be degraded to provide stoichiometric access to low-coordinate phosphorus species. The ability for successful P-Ch transfer relies on using a bulky m-terphenyl group at phosphorus that provides enough steric bulk to kinetically stabilize the phosphorus centre, but also accommodating enough to allow …

The Addition Of Alkynes To Low-Valent Silicon Compounds: A Mechanistic Study, Andrew T. Henry

Electronic Thesis and Dissertation Repository

The mechanism for the addition of alkynes to low-valent silicon compounds was investigated in this thesis using a cyclopropyl alkyne mechanistic probe (1.31). The addition of alkyne 1.31 to the asymmetrically-substituted disilene 1.37 was investigated. The structures of the products obtained indicate the reaction proceeds through a stepwise mechanism with a biradical intermediate and the dipole moment of the disilene bond was not sufficient to alter the reaction mechanism.

The addition of alkyne 1.31 to the NHC-stabilized silylene 1.38 was also investigated. The structure of the product formed in the reaction lead to two conclusions: that silylene 1.38 …

Developing Structure-Activity-Relationships For Metal-Ligand-Cooperative (Mlc) Complexes Using Pr2nr′2 Ligands, James M. Stubbs

Electronic Thesis and Dissertation Repository

Exploring efficient and environmentally-friendly routes to synthesize molecules is critical for the pharmaceutical and fine chemical industries. One method is to study current catalytic methods to increase selectivity and performance for challenging reactions. Inclusion of an intramolecular acid/base site on the ligand manifold of an organometallic complex has allowed for new mechanistic pathways and enhanced reactivity. This thesis delves into understanding organometallic complexes in catalysis by systematic tuning the ligand properties. Synthesis of P^R₂N^R′₂ ligands was performed to enable the systematic tuning as R and R′ alter the electronic and steric properties of the primary …