DIIRON CHEMISTRY IN MACROCYCLIC DICARBOXYLATE LIGANDS

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Proteins enforce structural integrity via their polypeptide "backbone", which serves as a matrix controlling the access to and the orientation of residues in the active site. Duplication of these features in model complexes using simple carboxylate ligands is often difficult due to their kinetic lability and large variety of binding modes to metal ions. This research proposal describes a series of cyclophanes with two craboxylate moieties positioned in an endo-fashion and oriented to bind two metal ions in a bidentate bridging mode. It is proposed that such a series of cyclophane dicarboxylate ligands would provide a pocket that would sterically protect the dimetallic core and offer increased kinetic stability via the macrocyclic effect. The role of these ligands is to afford dimetallic models for a variety of biologically relevant metalloproteins.