Synthesis of Novel Chelating N-Heterocyclic Carbenes and Their Heavier Analogues as Tools in Coordination Chemistry

新型螯合 N-杂环卡宾及其较重类似物作为配位化学工具的合成

• 批准号: 279353839
• 负责人: Professor Dr. Matthias Drieß
• 金额: --
• 依托单位: Arbeitsgruppe Metallorganische Chemie und Anorganische Materialien
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2023-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/279353839?language=en
• 关键词: Synthesis; Novel; Chelating; Heterocyclic; Carbenes

N-Heterocyclic carbenes (NHCs) have been attracting worldwide interest because of their considerable potential in coordination/organometallic chemistry, catalysis and materials science. In recent years, stable N-heterocyclic silylenes (NHSis), the silicon analogues of NHCs, are no longer laboratory curiosities but valuable building blocks for new functional silicon compounds. Particularly, NHSis can act as very effective sigma-donor ligands toward low-valent main group elements and transition-metals to form novel types of complexes with currently unknown and promising chemical behavior. The goal of this project is to develop new NHC and NHSi chelate systems that serve as effective supporting ligands for the stabilization of currently unknown main-group (Si, Ge, Sn, Pb, B, Al, Ga, etc.) and transition metal (Mn, Fe, Co, Ni, etc.) complexes. The complexes are expected to show particular reactivities because of the unusual low oxidation states of the central atoms. The resulting chelate ligand supported low-valent compounds are highly reactive with respect to the activation of small molecules and thus useful for chemical transformations of substrates which are otherwise hard to achieve. Moreover, the silylene-containing target systems, featuring at least one divalent silicon center, are even capable to facilitate the activation of small molecules without the presence of a metal (‘metal-free’) and can lead to value-added coupling products of organic substrates such as the heterocoupling of CO and isocyanides to give ketimines. Not only for better understanding but eventually to derive at the level of predicting their steering role in coordination chemistry, the synthesis and reactivity patterns of NHC and NHSi chelate ligands,related sigma-donor systems such as phosphine, pyridine and even those of the currently unknown bis-phosphinidene and bis-borylene moieties are included in this investigation.

n -杂环碳因其在配位/有机金属化学、催化和材料科学等方面的巨大潜力而引起了世界范围内的广泛关注。近年来，稳定的n -杂环硅烯（NHSis）， NHCs的硅类似物，不再是实验室的好奇心，而是新的功能硅化合物的宝贵基石。特别是，NHSis可以作为非常有效的西格玛供体配体，用于低价主族元素和过渡金属，形成具有目前未知和有希望的化学行为的新型配合物。该项目的目标是开发新的NHC和NHSi螯合体系，作为目前未知的主基团（Si, Ge, Sn, Pb， B, Al， Ga等）和过渡金属（Mn, Fe, Co， Ni等）配合物的有效支撑配体。由于中心原子不寻常的低氧化态，这些配合物预计会表现出特殊的反应活性。所得到的螯合配体支持的低价化合物对小分子的活化具有高度活性，因此对底物的化学转化有用，否则很难实现。此外，含有硅烯的靶体系具有至少一个二价硅中心，甚至能够在没有金属存在的情况下促进小分子的活化（“无金属”），并且可以导致有机底物的增值偶联产物，例如CO和异氰酸酯的异偶联以产生酮胺。不仅是为了更好地理解，而且最终在预测它们在配位化学中的指导作用的水平上得出，NHC和NHSi螯合配体的合成和反应模式，相关的sigma给体系统，如膦，吡啶，甚至是目前未知的双膦烯和双硼基部分，都包括在本研究中。