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

这个联合项目的主要目的是结合自然界的两种策略来介导多电子氧化还原转化：利用(i)双金属位点的氧化还原库和（it）金属配位的苯氧基自由基。为此，将合成具有两个金属结合酚酸基团的新型双核配体支架，并详细研究其双金属配合物（主要是二镍、二铜和二锌配合物）的氧化还原性能。该项目将侧重于阐明双核物质在不同氧化水平下的电子结构，并通过微调配体支架来调节金属和配体氧化还原过程的顺序。我们的主要目标是制备高度预组织的双核金属配合物，具有可变的内源性和外源性桥接基团和可变的末端配位，以提供总共四个电子（两个来自金属中心，两个来自每个末端酚酸单位），并研究它们在与生物学相关的氧化/氧化反应中的潜力，最终对工业过程具有重要意义。我们的目标是应用新发现的化学知识来更好地理解选定的一类金属酶（典型的例子是半乳糖氧化酶）的性质，并通过在单个人工分子系统中结合两种自然功能原理来为生物启发催化剂铺平新的道路。

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.