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

受挫刘易斯对（FLP）是由于位阻作用而不能形成中和加合物的刘易斯酸和刘易斯碱的化合物或混合物。自2006年被发现以来，它们已经发展成为合成有机化学和分子有机催化界的一个独立研究领域。由于它们的高反应性，FLP可以激活小分子，如氢。因此，它们为无过渡金属加氢催化剂和新催化工艺的发展提供了巨大的潜力。为了开发FLP的潜力，并在此基础上长期开发新的化学工艺，它们的多相化非常重要。到目前为止，在科学和专利文献中还没有提到，这个主题将在这个项目中通过多孔聚合物中的受挫刘易斯对概念来解决。多孔聚合物或有机框架非常适合于FLP的异质化，因为由于模块化的概念，至少一个FLP伙伴可以用作单体，从而形成多孔网络的一个组成部分。通过不同的合成路线，合成了具有路易斯酸性中心或碱性中心的多孔聚合物。然后，这些聚合物被用作固体载体，使易于接近的活性中心最大限度地分散，并与选定的分子路易斯伙伴一起从溶液中加载。利用合适的位阻和Lewis中心的电子结构，在多孔网络内形成了FLP。重点研究了负载前后网络的结构、化学和热性能，并进行了催化实验。异质FLP的催化活性是根据从文献中已知的分子种类的液相测试反应来研究的。重点是亚胺、贫电子烯烃和多环芳烃的氢化反应。除氢活化外，还研究了二氧化碳的活化，二氧化碳是已知的少数分子FLP。此外，证明了氢和二氧化碳的非均质过渡无金属气相活化的概念。总的来说，该项目为迄今为止以合成有机化学为主的FLP研究领域的跨学科扩展奠定了基础，并启动了新的激励机制。它结合了基于FLP的新型功能材料的制备和表征及其构效关系的进一步基础研究与多相催化新技术的应用相关发展。

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.