Synthesis and Study of Non-Keukule Molecules

非Keukule分子的合成与研究

• 批准号: 9019814
• 负责人: Paul Dowd DECEASED
• 金额: $ 29.5万
• 依托单位: University of Pittsburgh
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1991
• 资助国家: 美国
• 起止时间: 1991-01-01 至 1994-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9019814&HistoricalAwards=false
• 关键词: Synthesis; Study; Non; Keukule; Molecules

This grant from the Organic Dynamics Program supports the continuing work of Professor Paul Dowd at the University of Pittsburgh. The research is directed to the synthesis of reactive intermediates which possess two unbonded electrons. The project will further characterize the electronic state of these biradicals. There is an interest in biradical intermediates, since they are involved in ferromagnetism and some biological processes. Dr. Dowd's research will provide a bridge between theory and experiment in the area of biradical chemistry. In one project, the electronic structure of tetramethyleneethane will be probed experimentally in a rigid molecule. Previous studies in flexible systems have suggested that this biradical is a triplet, while molecular orbital calculations indicate a singlet. The use of a rigid system here will allow for an adequate comparison to the molecular orbital calculations. Simple molecular orbital theory predicts that non-alternant biradicals will be ground state singlets, yet this has not been tested. As a test of this theory, these biradicals will be generated and studied by spectrocopic methods and chemical trapping. Two other biradical systems, semilocalized biradicals and methylenecyclobutanone biradical, are to be prepared and characterized as well. Since biradicals are important intermediates in several chemical reactions, this work should add to our ability to understand and predict the course of reactions.

有机动力学计划的这笔赠款支持 保罗·多德教授继续在哥伦比亚大学 匹兹堡本研究的目的是合成反应性 具有两个未键合电子的中间体。项目 将进一步表征这些的电子状态 双自由基人们对双自由基中间体很感兴趣，因为 它们与铁磁性和某些生物过程有关。 多德博士的研究将为理论和 在双自由基化学领域的实验。在一个项目中， 探讨了四亚甲基乙烷的电子结构 在刚性分子中进行实验。以前的研究在灵活的 系统已经表明，这种双自由基是三重态，而 分子轨道计算表明是单线态。的使用 严格的制度，这里将允许一个充分的比较， 分子轨道计算简单分子轨道理论 预测非交替双自由基将是基态 单态，但这还没有经过测试。作为对这一理论的检验， 这些双自由基将被产生并通过光谱学研究。 方法和化学捕集。另外两个双自由基系统， 半定域双自由基和亚甲基环丁酮双自由基， 来制备和表征。由于双自由基是 一些化学反应中的重要中间体，这项工作 应该会增加我们理解和预测 反应.