Low-Coordinate Germanium and Tin Compounds for Small Molecule Activation and Catalysis

用于小分子活化和催化的低配位锗和锡化合物

• 批准号: 421609377
• 负责人: Professor Dr. Shigeyoshi Inoue
• 金额: --
• 依托单位: Institut für Siliciumchemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2019
• 资助国家: 德国
• 起止时间: 2018-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/421609377?language=en
• 关键词: Low; Coordinate; Germanium; Tin; Compounds

Recent years showed significant interest to the field of main group element catalysis, which is considered as a sustainable alternative to the classical transition metal catalyzed transformations. The knowledge about activation of small molecules at a given metal center and its effective synthetic exploration are the prerequisites for the development of novel catalytic processes. The most recent studies demonstrated, that among various main group systems those based on low-coordinate group 14 metals can undergo not only transition metal-like reactions but also exhibit characteristic reactivity which may serve as a basis for novel catalytic transformations. Recently, we found that N-heterocyclic imine (NHI) supported low-coordinate silicon compounds show unique reactivity and are capable to activate sigma- and pi-bonds of small molecules under very mild reaction conditions. At this point, the transfer of this knowledge to heavier group 14 analogues with higher metallic character is very actual and important. The main objective of this project is to study novel rationally designed low-coordinate NHI stabilized germanium and tin compounds, such as tetrylenes, heavier alkene- and homo- and heteronuclear alkyne analogues, in small molecule activation reactions and their application in catalysis. As a well-structured approach based on our previous research experience and results, this study will have an essential impact on fundamental understanding of catalytic transformations at low-coordinate main group metal centers and prerequisites of catalytic activity. The work programme is divided into two main parts. Part A describes synthetic approaches to the target NHI-supported germanium and tin compounds. Part B includes detail description of the reactivity studies and practical development of catalytic transformations. The three-year research project is designed for two PhD students: one will work on germanium and another on tin chemistry.

近年来，人们对主族元素催化领域产生了浓厚的兴趣，认为主族元素催化是传统过渡金属催化转化的可持续替代品。了解特定金属中心小分子的活化及其有效的合成探索是开发新型催化工艺的先决条件。最近的研究表明，在各种主要基团体系中，基于低配位基团14的金属不仅可以发生过渡金属反应，而且还表现出特有的反应活性，这可能为新的催化转化提供基础。最近，我们发现n -杂环亚胺（NHI）负载的低配位硅化合物具有独特的反应活性，并且能够在非常温和的反应条件下激活小分子的sigma和pi键。在这一点上，将这一知识转移到具有更高金属性质的更重的14族类似物是非常实际和重要的。本课题的主要目的是研究新型合理设计的低配位NHI稳定锗锡化合物，如四烯、重烃、同核和异核炔类似物在小分子活化反应中的应用。作为一种基于我们以往研究经验和结果的结构良好的方法，本研究将对低坐标主基团金属中心催化转化的基本理解和催化活性的先决条件产生重要影响。工作方案分为两个主要部分。A部分描述了目标nhi支持的锗和锡化合物的合成方法。B部分包括反应性研究和催化转化的实际发展的详细描述。这个为期三年的研究项目是为两名博士生设计的：一名将研究锗化学，另一名研究锡化学。