Electron Transfer Mediated Reactions

电子转移介导的反应

• 批准号: 9200144
• 负责人: Silas Blackstock
• 金额: $ 17.76万
• 依托单位: Vanderbilt University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1992
• 资助国家: 美国
• 起止时间: 1992-05-01 至 1996-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9200144&HistoricalAwards=false
• 关键词: Electron; Transfer; Mediated; Reactions

This grant from the Organic Dynamics Program supports the work of Professor Silas C. Blackstock at Vanderbilt University. Electron transfer mediated fragmentations and rearrangements will be examined. In particular, fragmentations of nitrogen-containing substrates such as diazenes, nitroso compounds, and azooxides, and rearrangements of methylenecyclopropane and allyl vinyl ether will be examined under oxidative conditions. Short lived radical ion intermediates will be spectroscopically characterized by low temperature solid state and solution ESR methods. The structures of the radical ion intermediates will be engineered to enhance their lifetimes in order to allow their direct observations. Reaction rate measurements to determine electron transfer mediated rate accelerations and product analysis to evaluate mechanistic hypotheses will also be conducted. %%% The removal of an electron from an organic molecule frequently results in cleavage of the molecule or rearrangement of the connectivity of its atoms. In this project a variety of carbon and nitrogen containing substrates will be used to examine these reactions. These processes are energetically costly or nonexistant in the neutral precursors. This work will study the electron deficient intermediates directly in order to understand how electron transfer accelerates these reactions. Knowledge gained from this study will facilitate informed development of new electron transfer applications in organic chemistry.

有机动力学计划的这笔赠款支持范德堡大学 Silas C. Blackstock 教授的工作。 将检查电子转移介导的断裂和重排。 特别是，将在氧化条件下检查含氮底物（例如二氮烯、亚硝基化合物和偶氮氧化物）的断裂以及亚甲基环丙烷和烯丙基乙烯基醚的重排。 短寿命自由基离子中间体将通过低温固态和溶液 ESR 方法进行光谱表征。 自由基离子中间体的结构将被设计以延长其寿命，以便能够直接观察。 还将进行反应速率测量以确定电子转移介导的速率加速和产物分析以评估机械假设。 %%% 从有机分子中除去电子经常会导致分子断裂或原子连接性重新排列。 在该项目中，将使用各种含碳和氮的底物来检查这些反应。 这些过程的能源成本很高，或者在中性前体中不存在。 这项工作将直接研究缺电子中间体，以了解电子转移如何加速这些反应。 从这项研究中获得的知识将有助于有机化学中新电子转移应用的明智开发。