DIIRON CHEMISTRY IN MACROCYCLIC DICARBOXYLATE LIGANDS

蛋白质通过其多肽“骨架”来加强结构完整性，所述多肽“骨架”充当控制活性位点中残基的接近和取向的基质。在模型配合物中使用简单的羧酸配体复制这些功能往往是困难的，由于其动力学不稳定性和各种各样的结合模式的金属离子。本研究计划描述了一系列具有两个羧基部分的环番，其以内方式定位并以双齿桥接模式定向结合两个金属离子。有人提出，这样一系列的环蕃二羧酸配体将提供一个口袋，将空间保护的双金属核心，并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学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.