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

• 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

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项目的支持，研究有机金属化合物的电子转移过程。伴随着电子转移反应的分子结构重排正在被研究，重点是过渡金属有机金属配合物中金属-配体和金属-金属键的可逆形成和断裂，以及高电子富价金属-环戊二烯基化合物的几何变化。使用非配位氟基硼酸盐（FAB）型阴离子作为电解质，使自由基阳离子二聚化的研究成为可能。金属-金属键的形成和钌新世化学的复杂性是研究的目标。在传感器和其他设备中，用更耐热的真辛烯基标签取代二茂铁标签的可行性正在研究中。随着fab型阴离子的发展，基于双环和三环四胺的大的、高度亲脂性阳离子的制备正在进行，其目标是推进依赖于还原电化学的合成和机理研究。还讨论了使用含有三（吡唑基）硼酸酯配体的Rh和Ir化合物的阳离子来探测金属配体sigma键的可逆裂解，这一过程对催化具有重要意义。电子转移反应在自然界中无处不在，在光合作用、新陈代谢、氢和化石燃料的能源生产、药物和特种化学品的合成以及电池和传感器的操作等过程中发挥着重要作用。该项目对电子转移和分子水平结构变化之间的关系提供了基本的理解，以指导这些领域的发展。