Syntheses, structures & bonding of high oxidation state main-group & transition metal fluoride derivatives

本提案为合成和结构无机氟化学领域的基础研究寻求资助，其中包括主族元素和氧化态最高的重金属过渡金属元素的高活性氟化物和氧化物氟化物。所描述的物种都具有综合挑战性和高度空气敏感性，为这一战略领域的高能力实验人员提供了一个极好的培训场所。所处理的化合物通常处于化学稳定性的边缘，具有高能量和强氧化性，需要高度专业化的低温处理技术和化学惰性装置。这些化合物因其具有侵略性的化学行为、新颖的键和结构特征而引起基础化学家和应用化学家的兴趣。这些化合物跨越经典的2中心- 2电子和所谓的“高价”键，通常是高度配位的，大大超过了与经典的“八隅体规则”相关的价壳层的4个电子对。所提出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观念的新结构。本提案中涉及的一些氟化合物，特别是稀有气体化合物，是已知最强的氧化剂之一，是本提案中描述的一些其他新型高氧化态物质的前身。该计划提供的培训，技术和化学与工业和社会相关。尽管绝大多数商用氟化合物是有机的（例如，20-25%的药品含有至少一种氟），但制备这些化合物中的任何一种都需要使用无机氟化合物，例如HF、F2、BF3或SF4。无机氟化合物，如UF6、NF3、ClF3、SF6、HF、BF3和XeF2，对于国家核能发电、光伏材料、半导体材料、制冷剂、先进光学、制药和农业化合物、医学成像用18f放射性药物和微电子用蚀刻剂的持续存在和增长是绝对关键的（而且是不可替代的）。

This Proposal seeks funding for fundamental research in the field of synthetic and structural inorganic fluorine chemistry, and encompasses highly reactive fluorides and oxide fluorides of the main-group elements and of the heavy transition metal elements in their highest oxidation states. The described species are all synthetically challenging and highly air-sensitive, providing an excellent venue for the training of highly competent experimentalists in this strategic field. The compounds that are dealt with are frequently at the fringes of chemical stability and are highly energetic and strongly oxidizing, requiring highly specialized low-temperature handling techniques and chemically inert apparatus. Such compounds are of interest to the fundamental and applied chemist because of their aggressive chemical behaviours, novel bonding and structural features. These compounds span classical 2-centre - 2-electron and so-called "hypervalent" bonding and are often highly coordinated, greatly exceeding the 4 electron pairs in the valence shell that are associated with the classic "octet rule". The proposed chemistry, often at the edge of what is possible, will provide new structures that challenge, affirm and extend modern ideas of chemical bonding. A number of the fluorine compounds dealt with in this proposal, in particular noble-gas compounds, are among the strongest oxidants known and serve as progenitors to a number of other novel high-oxidation state species described in this Proposal. The training, technology and chemistry afforded by this program are relevant to industry and society. Although the vast majority of commercial fluorine compounds are organic (e.g., 20-25% of pharmaceuticals contain at least one fluorine), the preparation of any one of these compounds requires the use of inorganic fluorine compounds, e.g., 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 the Nation's nuclear power generation, photovoltaic materials, semiconductor materials, refrigerants, advanced optics, pharmaceutical and agricultural compounds, 18F-radiopharmaceuticals for medical imaging and etchants for microelectronics.