Molecular Electroanalytical Chemistry: New Directions in Structures and Reactions of Organometallic Radicals

分子电分析化学：有机金属自由基结构和反应的新方向

基本信息

批准号：
0411703
负责人：
William Geiger
金额：
$ 61.8万
依托单位：
University of Vermont & State Agricultural College
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2004
资助国家：
美国
起止时间：
2004-09-01 至 2008-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=0411703&HistoricalAwards=false
关键词：
Molecular Electroanalytical Chemistry New Directions

项目摘要

Professor William E. Geiger of the University of Vermont is supported by the Analytical and Surface Chemistry program to investigate electron transfer processes of organometallic compounds. Molecular structural rearrangements that accompany electron transfer reactions are being studied focusing on reversible making and breaking of metal-ligand and metal-metal bonds in transition metal organometallic complexes and geometric changes in highly electron rich, hypervalent metal-cyclopentadienyl compounds. The use of the non-coordinating fluoroarylborate (FAB) type anions as electrolyte is enabling the study of radical cation dimerizations. Metal-metal bond formation and complexities of ruthenocene chemistry are being targeted. The feasibility of replacing ferrocenyl tags with more thermally robust ruthenocenyl tags in sensors and other devices is under study. Following on the development of FAB-type anions, the preparation of large, highly lipophilic cations based on bicyclic and tricyclic tetraamines is being undertaken with the goal of advancing synthetic and mechanistic work that relies on reductive electrochemistry. Also being addressed is the use of cations of Rh and Ir compounds containing the hydrotris(pyrazolyl)borate ligand to probe the reversible cleavage of metal-ligand sigma bonds, a process which has important implications for catalysis.Electron transfer reactions are ubiquitous in nature and play an important role in processes such as photosynthesis, metabolism, the production of energy from hydrogen and fossil fuels, the synthesis of drugs and specialty chemicals, and the operation of batteries and sensors. This project is providing fundamental understanding of the relationship between electron transfer and molecular level structural changes to guide developments in these areas.

佛蒙特大学的William E. Geiger教授得到了分析和表面化学计划的支持，以研究有机金属化合物的电子转移过程。正在研究伴随电子转移反应的分子结构重排，重点是过渡金属有机金属配合物中的金属配体和金属金属键的可逆制造和破裂，以及高度电子，高价值金属金属含量的几何变化。当电解质的使用非协调的氟化硼酸酯（FAB）型含量是为了研究自由基阳离子二聚化。金属 - 金属键的形成和纯新世化学的复杂性是针对的。正在研究使用传感器和其他设备中更热的氟苯基标签代替铁氧基标签的可行性。随着Fab型阴离子的开发，进行了基于双环和三环四环胺的大型，高度亲脂的阳离子的制备，目的是推进依赖于还原性电化学的合成和机械工作。还包括使用含有氢化氢（吡唑基）硼酸盐配体的RH和IR化合物的阳离子的用法来探测金属 - 配体含量键键的可逆切割，这一过程对催化具有重要意义。电子转移在本质上是普遍存在的自然和诸如诸如流程的能量的重要作用，可以在流程中发挥作用，是元素的作用，是元素的作用，是元素的元素，元论的元素，元素，元素，元论，是元素的元素，是元素的元素，富有元素的作用。燃料，药物和特种化学物质的合成以及电池和传感器的运行。该项目正在提供对电子传递与分子水平结构变化之间关系的基本理解，以指导这些领域的发展。