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:
- 金额:$ 61.8万
- 依托单位:
- 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:
- 关键词:
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。
项目成果
期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
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William Geiger其他文献
William Geiger的其他文献
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{{ truncateString('William Geiger', 18)}}的其他基金
Applications of Alkynyl-linked Transition Metal Compounds on Chemically Modified Electrodes
炔基过渡金属化合物在化学修饰电极上的应用
- 批准号:
1565541 - 财政年份:2016
- 资助金额:
$ 61.8万 - 项目类别:
Continuing Grant
New Redox Tags For Bioorganometallic Chemistry and Electrode Modification
用于生物有机金属化学和电极修饰的新型氧化还原标签
- 批准号:
1212339 - 财政年份:2012
- 资助金额:
$ 61.8万 - 项目类别:
Standard Grant
New Organometallic Radical-Cation Based Homogeneous and Heterogeneous Reactions and Materials
新型有机金属自由基-阳离子基均相和多相反应及材料
- 批准号:
0808909 - 财政年份:2008
- 资助金额:
$ 61.8万 - 项目类别:
Continuing Grant
Electrochemical Studies of Important Organometallic Compounds in New Types of Electrolytes
新型电解质中重要有机金属化合物的电化学研究
- 批准号:
0092702 - 财政年份:2001
- 资助金额:
$ 61.8万 - 项目类别:
Continuing Grant
Electron - Transfer Induced Changes in Ligand Hapticity and Reactivity
电子转移引起的配体触觉和反应性变化
- 批准号:
9705763 - 财政年份:1998
- 资助金额:
$ 61.8万 - 项目类别:
Standard Grant
Electrochemistry and Spectroelectrochemistry of Organometallic Compounds
有机金属化合物的电化学和光谱电化学
- 批准号:
9416611 - 财政年份:1995
- 资助金额:
$ 61.8万 - 项目类别:
Continuing Grant
Homogeneous and Heterogeneous Electron-Transfer Reactions
均相和非均相电子转移反应
- 批准号:
9116332 - 财政年份:1992
- 资助金额:
$ 61.8万 - 项目类别:
Continuing Grant
Electrochemical Investigations of Multiple Electron TransferReactions of Organometallic Compounds
有机金属化合物多电子转移反应的电化学研究
- 批准号:
8603728 - 财政年份:1986
- 资助金额:
$ 61.8万 - 项目类别:
Continuing Grant
Electrochemical Studies of Organometallic Pi-Compounds (Chemistry)
有机金属 Pi 化合物的电化学研究(化学)
- 批准号:
8303974 - 财政年份:1983
- 资助金额:
$ 61.8万 - 项目类别:
Continuing Grant
Electrochemical Studies of Structural Consequences of Organometallic Electron-Transfer Reactions
有机金属电子转移反应结构后果的电化学研究
- 批准号:
8004242 - 财政年份:1980
- 资助金额:
$ 61.8万 - 项目类别:
Continuing Grant
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Standard Grant
Improvements in the Electroanalytical Chemistry Curriculm
电分析化学课程的改进
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8015939 - 财政年份:1980
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Standard Grant
Electroanalytical Chemistry Curriculum Revision
电分析化学课程修订
- 批准号:
7814123 - 财政年份:1978
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$ 61.8万 - 项目类别:
Standard Grant
Surface Effects in Electroanalytical Chemistry
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- 批准号:
7423579 - 财政年份:1974
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$ 61.8万 - 项目类别:
Standard Grant
Organometallic Electroanalytical Chemistry
有机金属电分析化学
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7002043 - 财政年份:1971
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Standard Grant