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

该提案寻求为合成和结构无机氟化学方面的几个项目提供资金，这些项目包括主族元素的高活性氟化物和氧化物氟化物，以及几种处于最高氧化态的重金属过渡金属元素。所描述的物种都对空气高度敏感，具有综合挑战性，为培训高能力的实验者提供了一个极好的场所。所处理的化合物经常处于化学稳定性的边缘，因此是高能(吸热)的，并且在性质上通常是强氧化性的，需要高度专业化的低温处理技术和化学惰性处理设备。所描述的化合物对化学家来说是基本感兴趣的，因为它们具有高活性的性质以及它们所显示的新颖的成键和结构特征/几何结构。这些结构跨越经典的(2-中心-2电子)键和所谓的“超价”键，并且是高度配位的，通常大大超过价层中通常与经典的“八重规则”相关的4个电子对。拟议中的化学通常处于可能的边缘，它将提供挑战、肯定和扩展现代结合想法的新结构。本提案中涉及的一些氟化合物，特别是惰性气体化合物，也是已知的最活跃(氧化)物种之一，并且是本提案中描述的一些新的高氧化态物种的前体。在该计划中开发的技术和化学，以及PI以前资助的NSERC发现赠款，一直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)显像剂的人相关。*氚的基本氟化物和氟化物氧化物化学与铀再浓缩循环直接相关，与世界上老化的气体扩散厂退役和清理的环境问题直接相关，这些工厂已用于乏核燃料的再浓缩。

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.