FOR 5215:  Bioinspired Oxidation Catalysis with Iron Complexes

• Subject Area: Chemistry
• Term: since 2022
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 445916766

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.

• DFG Programme: Research Units

Projects

• Advanced X-ray Spectroscopic Approaches for the Characterization of High-Valent Iron Intermediates (Applicant DeBeer, Ph.D., Serena )
• Coordination Funds (Applicant Glaser, Thorsten )
• From Generation of Peroxo and High-Valent Diiron Complexes to Enantioselective C-H Oxidation Catalysts (Applicant Glaser, Thorsten )
• Mechanistic insights into formation and oxidation catalysis of/by FeIV=O and FeV=O: effects of spin state, redox active quinol or oxygen-rich ligands (Applicant Ivanovic-Burmazovic, Ivana )
• Merging Bioinorganics and Organometallics: NHC-Ligated Iron-Oxo and Iron-Peroxo Complexes for Catalytic C-H Activation and Functionalization (Applicant Meyer, Franc )
• Preventing and Understanding Autooxidation and Side Reactions and Providing a Second Coordination Sphere: Immobilized High Valent Iron Complexes for CH Activation Studies (Applicant Daumann, Lena )
• Spectroscopic and Theoretical Elucidation of Oxygen-Activating Transition Metal Centers – Developing Magnetic Raman Spectroscopy as a new Experimental Method (Applicant Neese, Frank )
• Towards a better understanding of the reactivity of nonheme iron-oxido systems (Applicant Comba, Peter )
• Understanding and advancing the reactivity of biomimetic models for mononuclear non-heme iron enzymes (Applicant Limberg, Christian )

• Spokesperson: Professor Dr. Thorsten Glaser