Hydrogen Bonding Cavity Motifs about Metal Ions

金属离子的氢键空腔基序

• 批准号: 6734740
• 负责人: Andrew S. Borovik
• 金额: $ 25.39万
• 依托单位: UNIVERSITY OF KANSAS LAWRENCE
• 依托单位国家: 美国
• 财政年份: 1994
• 资助国家: 美国
• 起止时间: 1994-04-01 至 2007-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6734740
• 关键词: X ray crystallography; active sites; binding sites; catalyst; chemical models; chemical reaction; chemical structure function; coulometry; free radical oxygen; hydrogen bond; infrared spectrometry; interferometry; intermolecular interaction; ions; ligands; metal complex; metalloproteins; nuclear magnetic resonance spectroscopy; protein structure; protein structure function

DESCRIPTION (provided by applicant): The aim of the research in this proposal is to construct microenvironments (secondary coordination spheres) about metal ions to direct their chemistry. A bio-inspired approach is utilized that incorporates principles of molecular architecture found in the active sites of metalloproteins. New modular multidentate ligands have been developed that create rigid organic frameworks around coordinatively unsaturated metal ions. These ligands position hydrogen bond (H-bond) donating or accepting groups proximal to metal centers, forming specific microenvironments. We will investigate how H-bond frameworks regulate the structural and reactivity of metal complexes with terminal oxo ligands and bis(mu-oxo) motifs. A special aspect of this work is consideration of H-bonds in dioxygen and C-H bond activation by metal complexes. Long term goals of this research include developing structure-function relationships in metal-assisted oxidative catalysis. Metalloproteins perform chemical reactions that have yet to be achieved in synthetic systems. This chemical versatility follows at least in part from the ability of the proteins to regulate the reactivity of their metal centers by adjustments of their microenvironment. Thus the function and dysfunction of metalloproteins can be understood in the context of changes in their microenvironments. This type of analysis necessitates basic reactivity studies in which the effects of single components can be analyzed individually as described herein. The systems outlined in this proposal can control the molecular components that define the structure around the metal ion(s), thus permitting the development of complexes whose activity can be tailored to a particular function. The ability to fine-tune the molecular design of the external ligand-binding site is beneficial for constructing microenvironments about reactive species. This allows for the systematic study of structure function relationships that can lead to a fundamental understanding of chemical and biological processes.

描述（由申请人提供）：该提案中研究的目的是构建有关金属离子的微环境（次要配位球），以指导其化学。采用了一种生物启发的方法，该方法结合了金属蛋白活性位点的分子结构原理。已经开发了新的模块化多齿配体，可在协调不饱和的金属离子周围创建刚性有机框架。这些配体位置氢键（H键）捐赠或接受与金属中心接近的基团，形成特定的微环境。我们将研究H键框架如何调节金属复合物与末端氧配体和BIS（MU-OXO）基序的结构和反应性。这项工作的一个特殊方面是考虑金属配合物中的二氧化物和C-H键激活中的H键。这项研究的长期目标包括在金属辅助氧化催化中发展结构功能关系。 金属蛋白执行的化学反应尚未在合成系统中实现。这种化学多功能性至少部分来自蛋白质通过调整其微环境来调节其金属中心反应性的能力。因此，可以在其微环境变化的背景下理解金属蛋白的功能和功能障碍。这种类型的分析需要基本的反应性研究，其中可以按本文所述单独分析单个组件的效果。该提案中概述的系统可以控制定义金属离子周围结构的分子成分，从而允许其活性可以针对特定功能量身定制。微调外配体结合位点的分子设计的能力有益于构建有关反应性物种的微环境。这允许对结构功能关系进行系统的研究，从而导致对化学和生物过程的基本理解。