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

拟议的研究计划侧重于合成和结构无机氟化学领域的基础研究，包括主族高活性氟化物和氧化物氟化物，以及处于最高氧化态的重金属过渡金属元素。拟议中的化学通常处于可能的边缘，将提供挑战、肯定和扩展现代化学键概念的新化合物。将调查的具体领域包括惰性气体化学、溴、氙气、汞和铱的最高氧化态，以及硫-氮-氟化物化学。在稀有气体的情况下，寻找新的氙碳、氙氮和氪氧键是研究计划的重要目标。许多目标化合物是“超价”的，即它们是高度配位的，并且大大超过了与经典的“八重规则”有关的价层中的4个电子对。本研究项目中涉及的大多数氟化合物，如惰性气体化合物KrF2和XeF6，都是已知的最强的化学氧化剂，通常作为其他新的高氧化态物种的前体。要处理的化合物是高活性、高能量和强氧化性的化合物。它们对空气敏感，往往热不稳定，需要高度专业化的低温处理技术、化学惰性设备和广泛的物理技术来表征其分子结构。因此，这一研究计划提供的具有挑战性的化学为培训这一战略领域的高能力研究人员提供了一个极好的场所。该项目提供的培训、技术和新化学与学术界和工业界相关。虽然绝大多数商业氟化合物是有机的(例如，最广泛使用的药物化合物中约40%至少含有一个氟原子)，但这些化合物中的任何一种的制备都需要直接或间接地使用无机氟化合物，如HF、F2、BF3或SF4。无机氟化合物，如UF6、NF3、ClF3、SF6、HF、BF3和XeF2，对于加拿大核电工业的持续存在和发展，以及对生产光伏材料、半导体材料、制冷剂、先进光学、药物和农业化合物、用于医学成像的18F放射性药物和用于微电子的腐蚀剂，都是绝对关键的(且不可替代的)。**

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 xenon–carbon, xenon– (and krypton–) nitrogen and krypton–oxygen 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. **