DIIRON CHEMISTRY IN MACROCYCLIC DICARBOXYLATE LIGANDS

蛋白质通过多肽“骨架”来加强结构完整性，“骨架”作为基质控制活性位点残基的进入和取向。在使用简单羧酸配体的模型配合物中复制这些特征通常是困难的，因为它们的动力学不稳定性和与金属离子的多种结合模式。本研究计划描述了一系列具有两个羧酸基的环烷，这些环烷位于内端，并以双齿桥接方式结合两个金属离子。我们提出，这一系列的环烷二羧酸配体将提供一个口袋，将空间保护双金属核心和提供增加的动力学稳定性通过大环效应。这些配体的作用是为各种生物相关的金属蛋白提供双金属模型。

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.