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

合成主族和高氧化态过渡金属氟化物的结构和键合

• 批准号: 599-2006
• 负责人: Schrobilgen, Gary
• 金额: $ 7.29万
• 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: 2008
• 资助国家: 加拿大
• 起止时间: 2008-01-01 至 2009-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=388303
• 关键词: Syntheses; structure; bonding; main; group

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.

本提案寻求为合成和结构无机氟化学方面的若干项目提供资金，这些项目包括主族元素和若干处于最高氧化态的重过渡金属元素的高活性氟化物和氧化物氟化物。所描述的物种都是高度空气敏感和合成的挑战，提供了一个很好的场所，为培训高素质的实验人员。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，因为它们具有高度反应性的性质和它们显示的新颖的键合和结构特征/几何形状。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，通常大大超过通常与经典的“八隅体规则”相关联的价层中的4个电子对。拟议中的化学，往往在什么是可能的边缘，将提供新的结构，挑战，确认和扩展现代键合的想法。本提案中涉及的许多氟化合物，特别是稀有气体化合物，也是已知的最具反应性（氧化性）的物质，并作为本提案中描述的许多新的高氧化态物质的祖先。本项目中开发的技术和化学以及PI持有的先前资助的NSERC发现赠款与核医学以及使用18 F标记放射性药物作为PET成像剂的人员相关（正电子发射断层扫描）扫描。锝的基本氟化物和氧化物氟化物化学与铀的再利用直接相关，这些问题涉及浓缩循环以及围绕世界上用于乏核燃料再浓缩的老化气体扩散工厂的退役和清理的环境问题。