The development of selective PNP Ligand stabilized Co complex catalysts

选择性PNP配体稳定Co配合物催化剂的研制

• 批准号: 361806216
• 负责人: Professor Dr. Rhett Kempe
• 金额: --
• 依托单位: Arbeitsgruppe Anorganische Chemie II
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2017
• 资助国家: 德国
• 起止时间: 2016-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/361806216?language=en
• 关键词: development; selective; PNP; Ligand; stabilized

The sustainable handling of the resources of our planet is a central challenge of humankind. Chemistry with its high demand of diverse resources and loaded with negative connotations has the chance to play a forerunner role hereby; firstly, since chemical key expertise is needed and, secondly, to improve acceptance in society and to attract more young people to our science. Noble metals are rare and expensive and are used diversely, for instance as catalysts. Many 3d-metals (transition metals of the 4th period) are abundant and very inexpensive. The replacement of noble metals by abundantly available and inexpensive 3d-metals in diverse chemical applications serves the above discussed science philosophy. Aim of the project proposal is the development of novel cobalt complex-catalysts for catalytic reactions that have been mediated by noble metals so far.In our preliminary work, published in JACS (2x) and Angew. Chemie (1x), we could develop novel highly active cobalt catalysts for important catalytic reactions. We propose the following interlinked sup-projects.Hydrogenation: In preliminary work, we could show that cobalt catalysts are an interesting alternative to noble metal catalysts in the hydrogenation of C=O bonds. Right now, we do not understand how the catalytic cycle runs and how the substrates become activated at the cobalt complex. Thus, we plan mechanistic studies permitting then a more rational catalyst design. The broad scope of our cobalt catalyst system in ketone hydrogenation suggests the development of related chiral catalysts, which is planned by us. Alkylation reaction using alcohols: In our project related publications, we could demonstrate a certain potential of our Co catalyst class in alkylation reactions using alcohols as the alkylation agents. Consequently, we propose to investigate the alkylation of ketones, of methyl-azaarenes and of alcohols. Such reactions proceed more efficient in the presence of bases, which permits a simple catalyst activation.Novel reactions: One of the most interesting question in 3d-metal catalysis is the one for novel catalytic reactions, which cannot be mediated by noble metals. In our published preliminary work, we discovered selectivity profiles that have not been seen for noble metals yet. The development of novel reactions based on such a selectivity seems feasible. In addition, we are interested in a novel C-C coupling reaction. Non-published preliminary work indicates a potential of our Co catalyst in such a reaction.

以可持续方式处理我们星球的资源是人类的一项核心挑战。化学对各种资源的需求很高，而且充满了负面的内涵，因此有机会发挥先导作用;首先，因为需要化学关键专业知识，其次，提高社会的接受度，吸引更多的年轻人加入我们的科学。贵金属是稀有和昂贵的，并且被广泛使用，例如作为催化剂。许多3d金属（第四周期的过渡金属）是丰富的，非常便宜。在不同的化学应用中，用大量可用且廉价的3d金属替代贵金属，这符合上述科学哲学。该项目的目的是开发新型钴络合物催化剂，用于迄今为止由贵金属介导的催化反应。在我们的初步工作中，发表在JACS（2x）和Angew上。化学（1x），我们可以开发新型的高活性钴催化剂的重要催化反应。我们提出了以下相互关联的子项目。氢化：在初步工作中，我们可以表明，钴催化剂是一个有趣的替代贵金属催化剂在C=O键的氢化。目前，我们还不了解催化循环是如何运行的，以及底物如何在钴络合物中被激活。因此，我们计划进行机理研究，以便进行更合理的催化剂设计。我们的钴催化剂体系在酮加氢中的广泛应用表明我们正在计划开发相关的手性催化剂。使用醇的烷基化反应：在我们的项目相关出版物中，我们可以证明我们的Co催化剂在使用醇作为烷基化剂的烷基化反应中具有一定的潜力。因此，我们建议研究酮，甲基氮杂芳烃和醇的烷基化。这种反应在碱的存在下进行得更有效，这允许简单的催化剂活化。新型反应：3d-金属催化中最有趣的问题之一是新型催化反应，这不能由贵金属介导。在我们已发表的初步工作中，我们发现了尚未看到的贵金属的选择性概况。基于这种选择性的新反应的发展似乎是可行的。此外，我们还对一个新的C-C偶联反应感兴趣。未发表的初步工作表明我们的Co催化剂在这样的反应中的潜力。