Combining Bimetallic Scaffolds and Metal-Coordinated Phenoxyl Radicals for Multi Electron Transformations: A Step Beyond Nature

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The main objective of this joint project is to combine two of nature s strategies for mediating multi-electron redox transformations: using the redox reservoir of (i) bimetallic sites and (it) metal-coordinated phenoxyl radicals. To this end new binucleating ligand scaffolds that bear two metal-binding phenolate groups will be synthesized, and redox properties of their bimetallic complexes (mainly dinickel, dicopper and dizinc complexes) will be studied in detail. The project will focus on elucidating the electronic structures of the binuclear species in various oxidation levels and on modulating the sequence of metal- and ligand-based redox processes by fine-tuning of the ligand scaffolds. Our primary goal is to prepare highly preorganized binuclear metal complexes with variable endogenous and exogeneous bridging groups and variable terminal coordination to supply a total of four electrons (two from the metal centers and two from each terminal phenolate units) and to study their potential towards oxidation/oxygenation reactions of relevance to biology and of importance to industrial processes, ultimately, our goal is to apply newly discovered chemical knowledge to achieve a better understanding of the properties of a selected class of metalloenzymes (a typical example is galactose oxidase) and to pave new ways to bioinspired catalysts by combining two of nature s functional principles in a single artificial molecular system.