Applications of Fluorine and Highly Electronegative Fluorinated Ligands to the Syntheses of High-Oxidation-State Derivatives of the Main-Group and Transition Metal Elements

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The proposed research program focuses on fundamental research in the field of synthetic and structural inorganic fluorine chemistry, encompassing highly reactive fluorides and oxide fluorides of the main-group and heavy transition metal elements in their highest oxidation states. The proposed chemistry, often at the edge of what is possible, will provide new compounds that challenge, affirm and extend modern ideas of chemical bonding. Among the specific areas that will be investigated are noble-gas chemistry, the highest oxidation states of bromine, xenon, mercury and iridium, and sulfur-nitrogen-fluoride chemistry. In the case of the noble gases, the quest for new xenoncarbon, xenon (and krypton) nitrogen and kryptonoxygen bonds are important objectives of the research program. Many of the targeted compounds are “hypervalent”, i.e., they are highly coordinated and greatly exceed the 4 electron pairs in the valence shell that are associated with the classic "octet rule". Most of the fluorine compounds dealt with in this research program, such as the noble-gas compounds KrF2 and XeF6, are among the strongest chemical oxidants known and often serve as precursors for other new high-oxidation state species. The compounds that are to be dealt with are highly reactive, energetic and strongly oxidizing. They are air-sensitive and often thermally unstable, demanding highly specialized low-temperature handling techniques, chemically inert apparatus and a broad range of physical techniques for the characterization of their molecular structures. The challenging chemistry provided by this research program therefore provides an excellent venue for the training of highly competent researchers in this strategic field. The training, technology and new chemistry provided by this program are relevant to academia and industry. Although the vast majority of commercial fluorine compounds are organic (e.g., ~40% of the most widely used pharmaceutical compounds contain at least one fluorine atom), the preparation of any one of these compounds requires, directly or indirectly, the use of inorganic fluorine compounds such as HF, F2, BF3, or SF4. Inorganic fluorine compounds such as UF6, NF3, ClF3, SF6, HF, BF3, and XeF2 are absolutely critical (and without substitute) for the sustained existence and growth of Canada's nuclear power industry, and for the production of photovoltaic materials, semiconductor materials, refrigerants, advanced optics, pharmaceutical and agricultural compounds, 18F-radiopharmaceuticals for medical imaging and etchants for microelectronics. **