Date of Award
Chemistry and Biochemistry
Macdonald, Charles (Chemistry and Biochemistry)
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The oxidation state of an atom provides details into the number of electrons associated with it, as well as the chemistry of the atom. Phosphorus can exhibit a range of oxidation states such as; +1, +3, and +5. One of the main focuses of my research is to utilize phosphorus in the electron-rich +1 oxidation state to produce neutral P(I)-containing complexes that are analogous to polyphosphazenes. We have extended the class of P(I)-containing complexes from small molecules to the production of oligomers. Our work is novel in that we have found a general method that allows us to partially or completely substitute the nitrogen sites to form oligomers that are isoelectronic to that of the polyphosphazene and that will have different properties than the parent polymers. Our method is the first, and to date only, method that can produce such materials and the ease and generality of the approach suggests excellent developments in the near and distant future. Over the last two decades, N-heterocyclic phosphines have been an important class of compounds that has helped shape the development of modern main group chemistry. There have been numerous synthetic attempts to generate these species but usually involve harsh reaction conditions, long reaction times, multiple byproducts, or contain RedOX active anions. Herein, we have demonstrated the clean and spontaneous approach to generate N-heterocyclic phosphines in a high yielding, one-pot fashion. We have also established that the resulting bromophosphines have shown to be useful reagents for the generation of the corresponding N-heterocyclic phosphenium salts by several common methods of anion abstraction or metathesis reactions. We have also undertaken the task of generating new phosphorus containing heterocycles using alternative ligands that include oxygen and sulfur elements.
Farrar, Gregory, "Utilizing Phosphorus(I) Methods Towards Phosphorus(III) Heterocycles and Phosphorus(I) Macromolecules" (2012). Electronic Theses and Dissertations. 389.