Electron Transfer Mediated Reactions

这项来自有机动力学项目的拨款支持范德比尔特大学塞拉斯·c·布莱克斯托克教授的工作。电子转移介导的碎片和重排将被检查。特别是，含氮底物如二氮，亚硝基化合物和偶氮氧化物的碎片，以及亚甲基环丙烷和烯丙基乙烯醚的重排将在氧化条件下进行检查。短寿命自由基中间体将通过低温固相和溶液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提高它们的寿命，以便它们能够直接观察。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品分析，以评估机制假设。从有机分子中去掉一个电子常常会导致分子的分裂或其原子连通性的重新排列。在这个项目中，将使用各种含碳和含氮的底物来检查这些反应。这些过程在中性前体中要么能量昂贵，要么不存在。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促进有机化学中新的电子转移应用的知情发展。

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.