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

氟和高负电性氟化配体在合成主族和过渡金属元素高氧化态衍生物中的应用

• 批准号: RGPIN-2016-04561
• 负责人: Schrobilgen, Gary
• 金额: $ 4.44万
• 依托单位: McMaster University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=709346
• 关键词: Applications; Fluorine; Highly; Electronegative; Fluorinated

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.

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，包括主族的高反应性氟化物和氧化物氟化物以及处于最高氧化态的重过渡金属元素。拟议的化学通常处于边缘。的可能性，将提供挑战、肯定和扩展现代化学键合理念的新化合物，其中将研究的具体领域包括稀有气体化学、溴、氙的最高氧化态。汞和铱以及硫-氮-氟化物化学就惰性气体而言，寻找新的氙碳、氙（和氪）氮和氪氧键是许多目标化合物的重要目标。超价”，即它们高度配位，大大超过了与经典“八位组规则”相关的价壳中的 4 个电子对。本研究项目涉及的氟化合物，例如稀有气体化合物 KrF2 和 XeF6，属于已知最强的化学氧化剂，并且经常作为其他新的高氧化态物质的前体。要处理的化合物具有高度氧化性。它们对空气敏感且通常热不稳定，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，该研究项目提供的具有挑战性的化学为该战略领域高素质研究人员的培训提供了绝佳的场所。尽管绝大多数商业氟，但该项目提供的培训、技术和新化学与学术界和工业界相关。化合物是有机的（例如，约 40% 最广泛使用的药物化合物含有至少一个氟原子），这些化合物中的任何一种的制备都需要直接或间接使用无机氟化合物，例如 HF、F2、 BF3 或 SF4 等无机氟化合物对于加拿大核电工业的持续存在和发展以及光伏发电来说绝对至关重要（且无可替代）。材料、半导体材料、制冷剂、先进光学、制药和农业化合物、用于医学成像的 18F 放射性药物和蚀刻剂微电子学。