Radical Cage Effects in Organometallic Chemistry and Reactions of Molybdocenes in Aqueous Solution

有机金属化学中的自由基笼效应和二茂钼在水溶液中的反应

• 批准号: 0093869
• 负责人: David Tyler
• 金额: $ 35.4万
• 依托单位: University of Oregon Eugene
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-04-01 至 2004-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0093869&HistoricalAwards=false
• 关键词: Radical; Cage; Effects; Organometallic; Chemistry

Dr. David Tyler of the Department of Chemistry, University of Oregon (Eugene), is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Division of Chemistry to investigate (i) the chemistry of radical species and (ii) the chemistry of molybdenocenes in aqueous media. In the first part the PI will examine radical pathways in mechanisms and in syntheses, that are a dominant theme in organometallic chemistry. Specifically, he will investigate cage effects in radical chemistry and explore the role of the solvent cage so as to achieve a fuller understanding of radical systems. He will employ femtosecond laser pump-probe techniques to probe the short-lived radical cage pairs and to assess cage reactivity. In the second part, the PI will investigate the reactivity of molybdenocenes in aqueous solutions to study the catalysis of vinyl polymerization reactions, nitrile hydrolyses, hydrogenation reactions, ethylene glycol synthesis, and Reppe chemistry.Students working on the projects will gain excellent training in a diverse set of skills such as syntheses, laser spectroscopy and dynamics, photochemistry, among others.They will be well equipped to make significant contributions to research and education. The results of the first part of the project will help improve our overall understanding of radical reactions; results from the second part will have a great impact on future developments of green chemistry.

俄勒冈大学(尤金)化学系的David Tyler博士在化学系无机、生物无机和有机金属化学计划的支持下，研究(I)自由基物种的化学和(Ii)水介质中钼烯的化学。在第一部分中，PI将研究机制和合成中的自由基途径，这是有机金属化学中的一个主要主题。具体地说，他将研究自由基化学中的笼子效应，探索溶剂笼子的作用，以实现对自由基体系的更全面的理解。他将使用飞秒激光泵浦-探测技术来探测短暂的自由基笼子对，并评估笼子的反应性。在第二部分，PI将研究钼烯在水溶液中的反应活性，以研究乙烯聚合反应、丁腈水解反应、氢化反应、乙二醇合成和Reppe化学的催化作用。从事这些项目的学生将获得各种技能的优秀培训，如合成、激光光谱和动力学、光化学等。他们将为研究和教育做出重大贡献。项目第一部分的结果将有助于提高我们对自由基反应的整体理解；第二部分的结果将对未来绿色化学的发展产生重大影响。