New Oxidation Catalysts Comprising Mesoionic Carbenes as Potentially Cooperative Ligands

包含介离子卡宾作为潜在协同配体的新型氧化催化剂

• 批准号: 202054744
• 负责人: Dr. Monika Lindner
• 金额: --
• 依托单位: School of Chemistry and Chemical Biology
• 依托单位国家: 德国
• 项目类别: Research Fellowships
• 财政年份: 2011
• 资助国家: 德国
• 起止时间: 2010-12-31 至 2013-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/202054744?language=en
• 关键词: New; Oxidation; Catalysts; Comprising; Mesoionic

In this research project I aim at developing new methods for the mild oxidation of organic compounds such as alcohols and alkanes, in particular of CO and CH bonds. For this purpose, new catalytic systems will be synthesized comprising redox-active ruthenium, iridium, and rhodium centers coordinated by new N-heterocyclic carbene ligands. These so-called abnormal carbenes show unique bonding properties due to a pronounced mesoionic character of the ligand which means that positive and negative partial charges are accommodated in the same heterocycle. This mesoionic character enables the ligand to respond to the electronic demand of the metal center important for oxidation catalysis. The new compounds will be investigated with respect to the potentially cooperative participation of the ligand in the catalyzed reaction. In this so-called bifunctional catalysis the ligands interact cooperatively with the metal center to facilitate the reaction which will be studied by mechanistic investigations. The ruthenium complexes will be examined as catalysts for the oxidation of alcohols, the iridium and rhodium complexes as catalysts for the functionalization of alkanes. Previous work in the group of Prof. Albrecht showed that complexes comprising abnormal carbenes as a class of mesoionic ligands feature remarkable properties, which are particularly powerful for oxidation catalysis, allowing for example to oxidize water to oxygen. Catalytic methods for the oxidation of alcohols and hydrocarbons under mild conditions are of great relevance for the pharmaceutical industry as well as for a better utilization of fossil fuel feedstocks (energy production) in terms of higher (atom-)economy and lower waste generation through an improved use of current resources.

在这个研究项目中，我的目标是开发新的方法，用于温和氧化有机化合物，如醇和烷烃，特别是CO和CH键。为此，将合成新的催化体系，其包含由新的N-杂环卡宾配体配位的氧化还原活性钌、铱和铑中心。这些所谓的异常卡宾显示出独特的键合性质，由于一个明显的介离子的配体，这意味着正和负的部分电荷被容纳在同一个杂环的字符。这种介离子特性使配体能够响应对氧化催化重要的金属中心的电子需求。新的化合物将被调查方面的潜在合作参与的配体在催化反应。在这种所谓的双功能催化中，配体与金属中心协同作用以促进反应，这将通过机理研究来研究。钌配合物将被检查作为催化剂用于醇的氧化，铱和铑配合物作为催化剂用于烷烃的官能化。Albrecht教授小组的先前工作表明，包含异常卡宾作为一类介离子配体的络合物具有显着的性质，其对于氧化催化特别强大，例如允许将水氧化为氧气。用于在温和条件下氧化醇和烃的催化方法对于制药工业以及对于通过改进现有资源的使用在更高的（原子）经济性和更低的废物产生方面更好地利用化石燃料原料（能量生产）具有重要意义。