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，对主要组元素催化的领域表现出了极大的兴趣，这被认为是经典过渡金属催化转化的可持续替代品。关于在给定金属中心及其有效合成探索的小分子激活的知识是开发新型催化过程的先决条件。最新的研究表明，在基于低坐标组的各个主要组系统中，14金属不仅可以经历过渡金属样反应，而且还表现出特征性的反应性，这可能是新型催化转化的基础。最近，我们发现N型型型亚胺（NHI）支持的低坐标硅化合物显示出独特的反应性，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，将此知识转移到具有较高金属特征的较重组的14个类似物非常实际和重要。该项目的主要目的是在小分子激活反应及其在催化中的应用中，研究新颖设计的低坐标NHI NHI稳定的NHI稳定的锗和Tin化合物，例如甲苯烯，较重的烯烃，烯烃和异核和异核碱类似物。作为基于我们以前的研究经验和结果的结构良好的方法，这项研究将对低坐标主要组金属中心的催化转化和催化活性的先决条件产生基本影响。工作计划分为两个主要部分。 A部分描述了靶标NHI支持的锗和锡化合物的合成方法。 B部分包括详细描述反应性研究和催化转化的实际发展。这项为期三年的研究项目是为两名博士学位学生设计的：一个将在锗上工作，另一个将在锡化学上工作。