Coordination Funds

能源生产的脱碳以及从石油、天然气和煤炭中高效、可持续地利用不可再生碳氢化合物资源，对于实现全球气候目标至关重要，这也是最近政治引发的公众讨论所要求的。在这方面，通过催化氧化和氧合反应对有机分子进行选择性功能化是从天然油气资源中制备基础和精细化学品以及合成复杂活性成分（如药品）的关键技术。因此，迫切需要建立新的可持续发展理念，利用环境友好且丰富的氧化剂，如在温和条件下的O2和H2O2，来合成高附加值产品。自然界经常使用具有铁离子活性位点的酶来选择性氧化有机底物。这些酶能够在O2活化过程中实现各种具有挑战性的反应。这些酶的催化循环已经在跨学科的努力中建立起来，结合了包括生物无机化学在内的不同领域的专业知识和方法。他们通过提供大量的结构和光谱模型，对酶的活性位点和中间体的分子和电子结构的阐明做出了巨大贡献。将从酶系统研究中获得的知识转移到新的均相催化剂（功能模型）的开发中，这是目前全世界都非常感兴趣的，也是本研究单元的重点。开发具有良好催化性能的生物均相催化剂用于烃类和更复杂的有机底物的氧化和氧合具有很高的学术和工业应用潜力。因此，本研究单元的最终目标是为使用环境友好的氧化剂（如O2和H2O2）进行氧化反应提供改进的生物启发均相催化剂，从而导致氧原子转移、氢原子提取和C-H键活化。这将通过收集申请者在生物无机模型化学、活性中间体的捕获和光谱分析、动力学分析、催化和理论建模方面的广泛专业知识来实现，以获得对活性中间体和六种已有生物激发氧化催化系统机制的详细了解。在生物启发模型系统中的这种机制洞察以及与相应的金属酶的比较应该允许在第一步i)确定模型系统反应性的局限性，这将最终允许ii)合理地提高它们的催化性能。

The decarbonization of the production of energy and an efficient and sustainable usage of non-renewable hydrocarbon resources from natural oil, gas, and coal is essential to achieve the global climate goals and has also been demanded in a politically-induced recent public dis¬cussion. In this respect, the selective functionalization of organic molecules by catalytic oxidation and oxygenation reactions is a key technology for the preparation of basic and fine chemicals from natural oil and gas resources, as well as for the synthesis of complex active ingredients, e. g. for pharmaceutical products. This defines an urgent need to establish new sustainable concepts for utilizing environmentally benign and abundant oxidants, such as O2 and H2O2 under mild con¬ditions for the synthesis of value-added products. Nature frequently uses enzymes with iron ions in the active sites for the selective oxidation of organic substrates. Such enzymes are capable of realizing a variety of challenging reactions during the course of O2 activation. The catalytic cycles of these enzymes have been established in interdisciplinary efforts combining expertise and methodologies from different fields including bioinorganic chemistry. They have strongly contributed to the elucidation of the molecular and electronic structures of the active sites and intermediates in the enzymes by providing a plethora of structural and spectroscopic modelsTransferring this knowledge gained from studies of the enzymatic systems to the development of new homogeneous catalysts (functional models) is presently of great interest worldwide and is the focus of this Research Unit. The development of bioinspired homogenous catalysts for the oxidation and oxygenation of hydrocarbons and more complex organic substrates with better catalytic performances has a high potential for academic and industrial applications.Thus, it is the ultimate goal of this Research Unit to provide improved bioinspired homogenous catalysts for oxidation reactions using environmentally benign oxidants such as O2 and H2O2 that results in oxygen-atom transfer, hydrogen atom abstraction, and C-H bond activation. This will be achieved by gathering the wide expertise of the applicants in bioinorganic model chemistry, trapping and spectroscopic analysis of reactive intermediates, kinetic analysis, catalysis, and theoretical modeling to obtain a detailed insight into the reactive intermediates and mechanisms of six already existing systems for bioinspired oxidation catalysis. This mechanistic insight in the bioinspired model systems and the comparison to the corresponding metalloenzymes should allow in the first step i) to identify the limitations in the reactivities of the model systems, which will finally allow ii) to rationally improve their catalytic performances.