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Unraveling and optimizing oxygen-oxygen bond formation pathways promoted by highly preoganized binuclear transition metal complexes

揭示和优化高度预组织双核过渡金属配合物促进的氧-氧键形成途径

基本信息

批准号：
164130766
负责人：
Professor Dr. Franc Meyer
金额：
--
依托单位：
Institut Català dInvestigació Quimica (ICIQ)
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2010
资助国家：
德国
起止时间：
2009-12-31 至 2013-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/164130766?language=en
关键词：
Unraveling optimizing oxygen bond formation

项目摘要

The main goal of the project is to obtain a deep understanding of the different factors that influence the O-O bond formation reactions promoted by transition metal complexes. This understanding should then lead to the design and preparation of rugged and efficient water oxidation catalysts.To achieve this main goal it is proposed to prepare a family of highly preorganized binucleating pyrazolate based ligands and their Ru complexes. All the complexes will be thoroughly characterized from structural and spectroscopic point of view. Especially their redox properties will be studied in detail, since the water oxidation reaction involves multiple electron transfer processes. Higher oxidation states will be generated either chemically or electrochemically and their spectroscopic properties studied. Stability and reactivity of the complexes will be analyzed with a special attention to their water exchange reactions. The particular ligand design will allow to prepare complexes where the electronic properties as well as through-space interactions between the active groups can be controlled. This will enable to study and control the different reaction mechanisms that can potentially take place in the O-O bond formation reactions promoted by binuclear Ru complexes. Strong efforts will thus be devoted to study and understand reaction mechanism through which the O-O bond formation occurs in these systems, which includes a thorough kinetic analysis together with 18O labelling experiments. Catalytic systems will then be established and optimized, and the best catalysts in homogeneous phase will be heterogenized in inorganic solid supports. For this purpose new complexes, with intrinsically the same coordination properties but modified with an anchoring group, will be prepared and attached to inorganic oxides such as TiO2. Further extension of water oxidation chemistry to Fe and Mn complexes is also envisaged, but only in a preliminary manner while the Ru chemistry will be extensively developed and understood.

该项目的主要目标是深入了解影响过渡金属配合物促进的O-O键形成反应的不同因素。这种理解，然后导致坚固的和有效的水氧化catalysts.To实现这一主要目标的设计和制备提出了制备一个家庭的高度preorganized双核吡唑基配体和它们的钌配合物。所有的配合物将从结构和光谱的角度进行彻底的表征。特别是它们的氧化还原性能将被详细研究，因为水的氧化反应涉及多个电子转移过程。更高的氧化态将产生化学或电化学和他们的光谱性质进行了研究。配合物的稳定性和反应性将进行分析，特别注意它们的水交换反应。特定的配体设计将允许制备复合物，其中可以控制活性基团之间的电子性质以及通过空间的相互作用。这将使研究和控制不同的反应机制，可能发生在双核钌配合物促进的O-O键形成反应。因此，将致力于研究和理解在这些系统中发生的O-O键形成的反应机理，其中包括彻底的动力学分析以及18 O标记实验。然后建立和优化催化体系，并将均相的最佳催化剂在无机固体载体中多相化。为此，将制备具有本质上相同的配位性质但用锚定基团改性的新络合物，并将其连接到无机氧化物如TiO 2上。还设想了水氧化化学向Fe和Mn络合物的进一步扩展，但仅以初步的方式，而Ru化学将被广泛开发和理解。