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

该提案寻求资助合成和结构无机氟化学领域的基础研究，包括主族元素和最高氧化态重过渡金属元素的高活性氟化物和氧化物氟化物。所描述的物种都是具有综合挑战性和高度的空气敏感性，提供了一个很好的场所，在这一战略领域的高度称职的实验人员的培训。所处理的化合物通常处于化学稳定性的边缘，并且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设备。这类化合物由于其具有强化学行为、新颖的化学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“超价”键合，并且通常高度配位，大大超过与经典的“八隅体规则”相关的价层中的4个电子对。拟议的化学，往往在什么是可能的边缘，将提供新的结构，挑战，确认和扩展化学键的现代思想。本提案中涉及的许多氟化合物，特别是稀有气体化合物，是已知的最强氧化剂之一，并作为本提案中描述的许多其他新的高氧化态物质的祖先。该计划提供的培训，技术和化学与工业和社会相关。尽管绝大多数商业氟化合物是有机的（例如，20-25%的药物含有至少一种氟），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、BF 3或SF 4。无机氟化合物，如UF 6，NF 3，ClF 3，SF6，HF，BF 3和XeF 2对于国家核能发电，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-放射性药物和微电子蚀刻剂的持续存在和增长至关重要（并且没有替代品）。

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.