Biologically inspired clusters: Synthetic control of structure and effects on reactivity

Abstract

Complex inorg. active sites perform challenging catalytic transformations in biol. systems, such as photosystem II and nitrogenase. The effect of cluster structure on the phys. and chem. properties of these active sites is not well understood. We have developed methodologies for the rational synthesis of tetranuclear homo- and hetero-metallic cluster models. Clusters with open coordination sites have been prepd. for small mol. activation. CH and CF oxygenation has been obsd. for putative terminal Fe-oxo species supported by tetranuclear clusters. Tetranuclear clusters with bridging fluoride and oxide interstitial ligands have been synthesized. Activation of nitric oxide by these clusters has been studied as a function of the interstitial ligand and metal oxidn. state. Implications for the function of biol. catalysts will be discussed.