Gated Electron Transfer in Copper(II)/(I) Systems

铜 (II)/(I) 系统中的门控电子转移

• 批准号: 0211696
• 负责人: David Rorabacher
• 金额: $ 38.5万
• 依托单位: Wayne State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-08-15 至 2006-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0211696&HistoricalAwards=false
• 关键词: Gated; Electron; Transfer; Copper; II

David Rohrabacher of Wayne State University and Michael Taschner of the University of Akron are supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program for research on effects of coordination site geometry on rates of electron transfer reactions of cuprous (Cu(I)) and cupric (Cu(II)) complexes. The main focus of the research will be to explore how ligands that constrain geometry about one or both copper centers influence the kinetics and mechanism of electron transfer (ET) between the two copper atoms. Main interest will be on the influence of solvent molecules on the ET rates of complexes involving macrocyclic and tripodal ligands, effects of trigonal and trigonal-pyramidal ligands that mimic coordination sites in specific copper proteins, and reorganization barriers in metastable intermediate species in reactions that involve macrocyclic ligands. Electron transfer reactions in related complexes containing both ruthenium and copper will also be investigated. New ligands to be used in each of these research areas will be synthesized at The University of Akron. Kinetic, electrochemical and spectroscopic studies will be performed at Wayne State University.Electron transfer reactions involving transition metal ions are of central importance in many areas of industrial chemistry and biochemistry and also in the emerging field of molecular electronics. This study focuses on rate processes that are known to be controlled, in greater or less degree, by conformational changes in the first coordination shells of the metal ions. This type of process has also been identified (sometimes quite tentatively) as playing a major role in many more-complex systems of practical interest. The relatively uncomplicated cases that are studied in this project are exceptionally suitable for developing and testing understandings that can then be applied to the more complicated cases that are of central importance in biological and technological applications.

韦恩州立大学的David Rohrabacher和阿克伦大学的Michael Taschner得到了无机、生物无机和有机金属化学计划的支持，他们研究了配位几何对Cuprous(Cu(I))和Cuprc(Cu(II))络合物的电子转移反应速率的影响。研究的主要焦点将是探索约束一个或两个铜中心的几何构型的配体如何影响两个铜原子之间的电子转移(ET)的动力学和机制。主要关注的是溶剂分子对大环和三脚架配体络合物ET速率的影响，模拟特定铜蛋白质配位位置的三角和三角-金字塔配体的作用，以及涉及大环配体的反应中亚稳态中间物种的重组障碍。还将研究同时包含Ru和铜的相关络合物中的电子转移反应。将在阿克伦大学合成用于每个研究领域的新配体。动力学、电化学和光谱研究将在韦恩州立大学进行。涉及过渡金属离子的电子转移反应在工业化学和生物化学的许多领域以及新兴的分子电子学领域都具有重要意义。这项研究集中在已知或多或少受金属离子第一配位壳层构象变化控制的速率过程。这种类型的过程也被认为(有时是相当试探性的)在许多具有实际意义的更复杂的系统中发挥着重要作用。这个项目中研究的相对不复杂的案例特别适合于开发和测试理解，然后这些理解可以应用于在生物和技术应用中具有核心重要性的更复杂的案例。