Chiral [1]Ferrocenophanes: Syntheses, Reaction Mechanisms, and Metallopolymers

手性 [1] 二茂铁：合成、反应机制和金属聚合物

• 批准号: RGPIN-2018-04273
• 负责人: Mueller, Jens
• 金额: $ 3.5万
• 依托单位: University of Saskatchewan
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=712835
• 关键词: Chiral; Ferrocenophanes; Syntheses; Reaction; Mechanisms

The development of organic polymers has clearly played a crucial role in the progress of our modern day life. Their applications range from shopping bags and flooring, to airplane components and electronic devices. However, as early as the 1950s scientists were intrigued by the idea to incorporate metals into polymers. After the first steps into this new field of science, it took more than four decades to overcome challenging problems. Over the last 25 years, the area of metal-containing polymers (metallopolymers) has witnessed tremendous progress; it is expected that these types of materials will be incorporated in devices in the decades to come. Despite the impressive progress, new monomers and polymerization methods are needed so that the enormous potential that the periodic table of elements offers for metallopolymers can be realized in the future. Our research program is in the area of synthetic organometallic chemistry, where we develop new metal-containing monomers and explore their polymerization behaviour. We apply ring-opening polymerization of strained sandwich species as an effective method to produce metallopolymers. The long-term objectives of the research program are: (i) to improve our fundamental knowledge about ring-opening polymerization of strained sandwich compounds, and (ii) to increase the scope of this method. In 2013 we published, and have since employed, a multistep synthesis that gives access to chiral, strained ferrocene derivatives ([1]ferrocenophanes). Because of their built-in chirality, these enantiopure [1]ferrocenophanes are a family of unique monomers. The properties of polymers are strongly dependent on their molecular weight and dispersity, not merely on their empirical formulas. For polymers with stereogenic centers, their macromolecular tacticity also has a significant effect on their physical properties. Hence, the ability to control the structures of macromolecules translates into controlling their properties. We propose to transform enantiopure [1]ferrocenophanes into a novel class of chiral metallopolymers. It is expected that their chiral structures will give rise to properties that are otherwise inaccessible. Reaction mechanisms are key to a deeper understanding of chemical reactivity and, therefore, key to a deeper understanding of chemistry in general. Even though the process of thermal ring-opening polymerization has been known for 25 years, its mechanism is still a mystery. We will use the chirality of our monomers to provide insight into the reaction mechanism of thermal ring-opening polymerization. Furthermore, we propose to expand the scope of these types of polymerizations by the development of a new polymerization process and by the synthesis of new monomers. In addition to the potential application of new materials, our program is an ideal training ground for HQP who will contribute to the Canadian economy in the future.

有机聚合物的发展显然在我们现代生活的进步中发挥了至关重要的作用。它们的应用范围从购物袋和地板，到飞机部件和电子设备。然而，早在20世纪50年代，科学家们就对将金属引入聚合物的想法很感兴趣。在进入这一新的科学领域的第一步之后，花了四十多年的时间来克服具有挑战性的问题。在过去的25年里，含金属聚合物（金属聚合物）领域取得了巨大的进步;预计这些类型的材料将在未来几十年内被纳入设备中。尽管取得了令人印象深刻的进展，但仍需要新的单体和聚合方法，以便在未来实现元素周期表为金属聚合物提供的巨大潜力。 我们的研究计划是在合成有机金属化学领域，在那里我们开发新的含金属单体，并探索其聚合行为。我们将应变三明治物种的开环聚合作为制备金属聚合物的有效方法。该研究计划的长期目标是：（i）提高我们对应变夹心化合物开环聚合的基础知识，以及（ii）增加这种方法的范围。 在2013年，我们发表了一个多步合成方法，并从那时起开始使用，该方法可以获得手性的、应变的二茂铁衍生物（[1]ferrocenophanes）。由于其内在的手性，这些对映体纯[1]二茂铁并吩是一类独特的单体。聚合物的性质强烈地依赖于它们的分子量和分散性，而不仅仅依赖于它们的经验式。对于具有立构中心的聚合物，其大分子的立构规整度对其物理性能也有显著的影响。因此，控制大分子结构的能力转化为控制它们的性质。我们提出了将对映体纯的[1]二茂铁并吩转化为一类新的手性金属聚合物。预计它们的手性结构将产生否则无法获得的性质。 反应机制是深入理解化学反应性的关键，因此也是深入理解一般化学的关键。尽管热开环聚合的过程已经知道了25年，但其机理仍然是一个谜。我们将使用我们的单体的手性，以提供洞察热开环聚合的反应机理。此外，我们建议通过开发新的聚合方法和合成新的单体来扩大这些类型的聚合的范围。 除了新材料的潜在应用外，我们的计划是HQP的理想培训基地，他们将在未来为加拿大经济做出贡献。