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.

可持续地处理地球资源是人类面临的主要挑战。化学对资源的多样性要求很高，并且充满负面含义，因此有机会发挥先行者的作用；首先，因为需要化学关键专业知识，其次，为了提高社会接受度并吸引更多年轻人接触我们的科学。贵金属稀有且昂贵，用途广泛，例如用作催化剂。许多 3d 金属（第四周期的过渡金属）储量丰富且非常便宜。在各种化学应用中用丰富且廉价的 3d 金属替代贵金属符合上述科学理念。该项目提案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。我们的初步工作发表在 JACS (2x) 和 Angew 上。 Chemie (1x)，我们可以开发用于重要催化反应的新型高活性钴催化剂。我们提出了以下相互关联的子项目。 氢化：在初步工作中，我们可以证明钴催化剂是 C=O 键氢化中贵金属催化剂的有趣替代品。目前，我们不了解催化循环如何运行以及钴配合物的底物如何被激活。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 催化剂类别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。这种反应在碱存在下进行得更有效，从而允许简单的催化剂活化。新颖的反应：3d-金属催化中最有趣的问题之一是新颖的催化反应，它不能由贵金属介导。在我们发表的初步工作中，我们发现了贵金属尚未发现的选择性特征。基于这种选择性的新反应的开发似乎是可行的。此外，我们对一种新颖的 C-C 偶联反应感兴趣。未发表的初步工作表明我们的钴催化剂在此类反应中具有潜力。