Syntheses structure and bonding in main-group and high oxidation state transition metal fluorides & oxide fluorides

这项建议为合成和结构无机氟化学方面的若干项目寻求资金，这些项目包括主要族元素和几种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。所描述的物种都是高度空气敏感和合成挑战性的，为训练高能力的实验人员提供了一个极好的场所。所处理的化合物通常处于化学稳定性的边缘，因此具有高能量（吸热），并且通常具有强氧化性，需要高度专业化的低温处理技术和化学惰性处理设备。所描述的化合物是化学家的根本兴趣，因为它们的高活性性质和新的键和结构特征/几何形状。这些结构跨越经典（2中心- 2电子）键和所谓的“高价键”，并且高度配位，通常大大超过了通常与经典“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、肯定和扩展现代键合思想的新结构。本提案中涉及的一些氟化合物，特别是稀有气体化合物，也是已知最具活性（氧化性）的化合物之一，是本提案中描述的一些新型高氧化态化合物的前身。在这个项目中开发的技术和化学物质，以及之前由PI持有的NSERC发现基金，与核医学和那些使用18f标记的放射性药物作为PET（正电子发射断层扫描）显像剂的人有关。锝的基本氟化物和氧化氟化物化学与铀再浓缩循环以及与世界上用于乏核燃料再浓缩的老化气体扩散厂的退役和清理有关的环境问题直接相关。

This proposal seeks funding for several projects in synthetic and structural inorganic fluorine chemistry that encompass highly reactive fluorides and oxide fluorides of the main-group elements and of several heavy transition metal elements in their highest oxidation states. The species that are described are all highly air-sensitive and synthetically challenging, providing an excellent venue for the training of highly competent experimentalists. The compounds that are dealt with are frequently at the fringes of chemical stability and are therefore highly energetic (endothermic) and are often strongly oxidizing in nature, requiring highly specialized low-temperature handling techniques and chemically inert handling apparatus. The compounds that are described are of fundamental interest to the chemist because of their highly reactive natures and the novel bonding and structural features/geometries they display. The structures span the classical (2-center - 2-electron) bonds and so-called "hypervalent" bonds and are highly coordinated, often greatly exceeding the 4 electron pairs in the valence shell that are normally 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 bonding ideas. A number of the fluorine compounds, in particular noble-gas compounds, dealt with in this proposal, are also among the most reactive (oxidizing) species known and serve as progenitors to a number of the novel high-oxidation state species described in this proposal. The technology and chemistry developed in this program and previously funded NSERC Discovery Grants held by the PI has been relevant to Nuclear Medicine and to those who use 18F-labelled radiopharmaceuticals as imaging agents for PET (positron emission tomography) scans.  The fundamental fluoride and oxide fluoride chemistry of technetium is of direct relevance to the uranium re-enrichment cycle and to the environmental issues surrounding the decommissioning and clean up of the world's aging gaseous diffusion plants that have been used for re-enrichment of spent nuclear fuels.