Frustrated Lewis-Pairs in porous polymer networks for the metal-free activation of small molecules and heterogeneously catalyzed hydrogenation

多孔聚合物网络中的受阻路易斯对用于小分子的无金属活化和非均相催化氢化

• 批准号: 320104743
• 负责人: Professor Dr. Marcus Rose
• 金额: --
• 依托单位: Fachgebiet Technische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/320104743?language=en
• 关键词: Frustrated; Lewis; Pairs; porous; polymer

Frustrated Lewis pairs (FLP) are compounds or mixtures of Lewis-acids and Lewis-bases which do not form neutralized adducts due to sterical hindrance. Since their discovery in 2006 they have evolved into an independent field of research within the synthetic organic chemistry and molecular organocatalysis community. Due to their high reactivity FLP can activate small molecules such as hydrogen. Thus, they pose enormous potential for the development of transition metal-free hydrogenation catalysts as well as new catalytic processes. To exploit the potential of the FLP and, on this basis on the long term, to develop new chemical processes, their heterogenization is of great importance. So far not mentioned in the scientific and patent literature, this topic will be addressed within this project by the concept Frustrated Lewis pairs in porous polymers. Porous polymers or organic frameworks are ideally suited for the heterogenization of FLP, since due to the modular concept, at least one FLP partner can be used as a monomer and thus, forms an integral part of the porous network. By different synthetic routes porous polymers with Lewis acidic or basic centers are synthesized. These polymers are then used as solid supports with maximum dispersion of the easily accessible active centers and loaded from solution with selected molecular Lewis partners. With a suitable sterical hindrance and electronic structure of the Lewis centers the FLP are formed within the porous networks. They are characterized with a focus on structural, chemical and thermal properties of the networks before and after loading and the catalytic experiments. The catalytic activity of the heterogenized FLP is investigated in accordance with test reactions in the liquid phase that are known from literature for molecular species. The focus is on the hydrogenation of imines, electron-poor alkenes as well as polycyclic aromatic hydrocarbons. Besides hydrogen activation also the activation of carbon dioxide is investigated which is known for a few molecular FLP. In addition, a proof of concept of the heterogeneously transition metal-free gas phase activation of hydrogen and carbon dioxide is aspired. Overall, the project establishes the foundation and initiates new incentives for the interdisciplinary extension of the research field of FLP that was so far dominated by synthetic organic chemistry. It combines further basic research on the preparation and characterization of new functional materials based on FLP and their structure-activity relationships with the application-related development of new technologies in heterogeneous catalysis.

受抑刘易斯对（FLP）是路易斯酸和路易斯碱的化合物或混合物，其由于空间位阻而不形成中和加合物。自2006年发现以来，它们已经发展成为合成有机化学和分子有机催化领域的一个独立研究领域。由于它们的高反应性，FLP可以活化小分子，如氢。因此，它们为开发无过渡金属氢化催化剂以及新的催化工艺带来了巨大的潜力。为了开发FLP的潜力，并在此基础上长期开发新的化学过程，它们的非均相化是非常重要的。到目前为止，在科学和专利文献中还没有提到，这个主题将在本项目中通过多孔聚合物中的受抑刘易斯对的概念来解决。多孔聚合物或有机框架理想地适用于FLP的异质化，因为由于模块化概念，至少一个FLP配偶体可以用作单体，从而形成多孔网络的组成部分。通过不同的合成路线合成了具有刘易斯酸性或碱性中心的多孔聚合物。然后将这些聚合物用作固体载体，使易于接近的活性中心最大化分散，并从溶液中加载选定的分子刘易斯配偶体。通过合适的空间位阻和刘易斯中心的电子结构，在多孔网络内形成FLP。它们的特点是，重点是负载和催化实验之前和之后的网络的结构，化学和热性能。根据在液相中的测试反应，从文献中已知的分子物种的多相化FLP的催化活性进行了研究。重点是亚胺、贫电子烯烃以及多环芳烃的加氢。除了氢活化之外，还研究了二氧化碳的活化，这对于一些分子FLP是已知的。此外，氢和二氧化碳的非均相无过渡金属气相活化的概念的证明是渴望的。总体而言，该项目为FLP研究领域的跨学科延伸奠定了基础，并启动了新的激励机制，迄今为止，FLP研究领域一直由合成有机化学主导。它结合了基于FLP的新功能材料的制备和表征及其结构-活性关系的进一步基础研究，以及多相催化新技术的应用相关开发。

项目成果

Porous Tin-Organic Frameworks as Selective Epimerization Catalysts in Aqueous Solutions

• DOI: 10.1021/acscatal.7b00806
• 发表时间: 2017-06-01
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Delidovich, Irina;Hoffmann, Andreas;Rose, Marcus
• 通讯作者: Rose, Marcus

A Bipyridine-Based Conjugated Microporous Polymer for the Ir-Catalyzed Dehydrogenation of Formic Acid

• DOI: 10.1021/acscatal.7b02425
• 发表时间: 2017-12-01
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Broicher, Cornelia;Foit, Severin R.;Palkovits, Regina
• 通讯作者: Palkovits, Regina

Grignard synthesis of fluorinated nanoporous element organic frameworks based on the heteroatoms P, B, Si, Sn and Ge

• DOI: 10.1039/c9py01193e
• 发表时间: 2019-09
• 期刊: Polymer Chemistry
• 影响因子: 4.6
• 作者: A. Kann;Andreas J. D. Krüger;M. Rose;P. Hausoul

Solid Molecular Frustrated Lewis Pairs in a Polyamine Organic Framework for the Catalytic Metal‐free Hydrogenation of Alkenes

• DOI: 10.1002/cctc.201701783
• 发表时间: 2018-04
• 期刊: ChemCatChem
• 影响因子: 4.5
• 作者: A. Willms;Hannah Schumacher;Tarnuma Tabassum;Long Qi;S. Scott;P. Hausoul;M. Rose