The development of selective PNP Ligand stabilized Co complex catalysts

可持续地处理地球资源是人类面临的一项核心挑战。化学以其对多种资源的高需求和承载着消极内涵的特点，有机会在此发挥先行者的作用；首先，因为化学关键专业知识是需要的，其次，提高社会的接受度，吸引更多的年轻人参与我们的科学。贵金属稀有而昂贵，用途广泛，例如用作催化剂。许多3d金属（第四周期过渡金属）储量丰富且价格低廉。在不同的化学应用中，用丰富而廉价的3d金属代替贵金属，符合上述讨论的科学哲学。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。在我们的初步工作中，发表在JACS （2x）和Angew。化学（1x），我们可以开发新的高活性钴催化剂用于重要的催化反应。我们提出以下相互关联的补充项目。加氢：在初步工作中，我们可以证明钴催化剂是贵金属催化剂在C=O键加氢中的一个有趣的替代品。目前，我们还不了解催化循环是如何运行的，以及底物是如何在钴络合物上被激活的。因此，我们计划进行机械研究，以实现更合理的催化剂设计。我们的钴催化剂体系在酮加氢中的应用范围很广，这表明我们计划开发相关的手性催化剂。醇烷基化反应：在我们项目相关的出版物中，我们可以证明我们的Co催化剂类在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、甲基氮杂环芳烃和醇的烷基化反应。这种反应在碱的存在下进行得更有效，因为碱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不能由贵金属介导的新型催化反应。在我们发表的初步工作中，我们发现了贵金属的选择性谱。基于这种选择性的新反应的发展似乎是可行的。此外，我们对一种新的C-C偶联反应很感兴趣。未发表的初步工作表明我们的Co催化剂在这种反应中的潜力。

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.