Transition metal organofluorine chemsitry

过渡金属有机氟化学

• 批准号: 371422-2009
• 负责人: Baker, Thomas
• 金额: $ 6.41万
• 依托单位: University of Ottawa
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2009
• 资助国家: 加拿大
• 起止时间: 2009-01-01 至 2010-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=434811
• 关键词: Transition; metal; organofluorine; chemsitry

Organofluorine compounds are useful as anesthetics, refrigerants, propellants for drug delivery, foam-blowing agents, water- and stain-repellants, lubricants and non-flammable solvents. While many of these compounds are non-toxic, they tend to persist in the environment and their manufacturing processes often involve significant quantities of toxic reagents such as chloro-alkenes and heavy metals such as antimony. In this research program, new metal organo-fluorine chemistry will be investigated with an eye to developing 'green' catalyzed routes to these important compounds. The chemistry will focus on easily prepared complexes of earth-abundant metals such as iron and nickel to mediate reactions of hydrofluoroalkenes generated by in situ reduction of non-toxic precursors. The resulting range of hydrofluorocarbon products will share many of the useful properties of perfluorocarbons but the reactive C-H bonds will guarantee their more rapid environmental degradation. Fluoropolymers such as Teflon and Viton also have many important uses such as non-stick coatings, heat- and wear-resistant seals and gaskets, fireproof insulation and 'breathable' clothing. These polymers are currently prepared using radical initiators either at high pressures or as aqueous emulsions using environmentally problematic surfactants such as perfluorooctanoic acid. This research program will conduct an in-depth study of the generation and reactivity of metal fluoro- and organo-fluorocarbene complexes (M=CHR, R = F, fluoroalkyl) to identify new catalysts for preparation of fluoropolymers with stereodefined microstructure. Exciting technical and intellectual challenges for the students include synthesis of air- and water-sensitive materials, sometimes at low temperatures, and hands-on access to rapid throughput experimentation, electrochemistry and computational chemistry facilities within the Centre for Catalysis Research and Innovation.

有机氟化合物可用作麻醉剂、制冷剂、药物输送推进剂、泡沫发泡剂、防水防污剂、润滑剂和不可燃溶剂。虽然这些化合物中许多是无毒的，但它们往往会在环境中持续存在，它们的制造过程往往涉及大量有毒试剂，如氯代烯和重金属，如锑。在这项研究计划中，将研究新的金属有机氟化学，着眼于开发这些重要化合物的绿色催化路线。化学将侧重于易于制备的富含稀土金属的络合物，如铁和镍，以调解无毒前体原位还原产生的氢氟烯的反应。由此产生的一系列氢氟碳化合物产品将分享全氟碳化合物的许多有用特性，但反应性C-H键将保证它们更快地在环境中降解。特氟龙和氟利昂等氟聚合物也有许多重要用途，如不粘涂层、耐热和耐磨密封件和垫圈、防火绝缘材料和“透气”服装。目前，这些聚合物是使用自由基引发剂在高压下制备的，或者作为水乳剂使用全氟辛酸等对环境有问题的表面活性剂来制备。这项研究计划将深入研究金属氟和有机氟卡宾(M=CHR，R=F，氟烷基)络合物的生成和反应活性，以确定用于制备具有立体结构的氟聚合物的新催化剂。对于学生来说，令人兴奋的技术和智力挑战包括合成对空气和水敏感的材料，有时是在低温下，以及亲手接触催化研究和创新中心的快速处理实验、电化学和计算化学设施。