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

佛蒙特大学的威廉·E·盖格教授得到了分析和表面化学项目的支持，该项目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络合物中金属-配体和金属-金属键的可逆形成和断裂，以及高电子含量的高价金属-环戊二烯化合物的几何变化。使用非配位的氟芳基硼酸盐(FAB)型阴离子作为电解液，使自由基阳离子二聚反应的研究成为可能。金属-金属键的形成和Ruthenocene化学的复杂性是目标。在传感器和其他设备中用更耐热的二茂铁基标签取代二茂铁基标签的可行性正在研究中。随着FAB型阴离子的发展，基于二环四胺和三环四胺的大分子、高亲油性阳离子的制备正在进行中，其目标是推进依赖于还原电化学的合成和机械工作。电子转移反应在自然界中普遍存在，在光合作用、新陈代谢、从氢和化石燃料中产生能量、药物和特种化学品的合成以及电池和传感器的工作等过程中发挥着重要作用。这个项目提供了对电子转移和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。

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.