Hydrogen Migration Reaction in Reactive Organic and Organometallic Intermediates

分子内氢迁移的机理基础 反应性有机和有机金属中间体中的反应将 被研究。低温基质隔离光谱，低温- 温度NMR光谱和时间分辨吸收 光谱学将用于建立重排途径， 来表征活性物质。有机卡宾，有机 氮烯和某些配位不饱和的16-电子 有机金属中间体包括等瓣类的 缺电子活性中间体，将被研究。在 在有机金属研究中，低温NMR将用于 遵循反应性烯丙基氢化物中间体的化学， 这些物质参与烯烃异构化过程。 铁、锇和钌金属原子将被纳入 有机金属中间体特别是，研究将 涉及烯丙基C-H和β C-H插入反应。在 有机研究，实验将集中在直接观察 卡宾和1，4-双自由基的氢迁移反应 时间分辨光谱学 %%% 有机动力学计划的这笔赠款支持以下工作： 威斯康星州大学的罗伯特·J·麦克马洪教授。的 氢原子如何在反应电子中迁移的细节， 缺陷有机和有机金属中间体， 将研究分子内过程。这些难以捉摸 中间体将在低温下进行研究， 光谱方法，以表征中间体 以及整个反应中的各个步骤。反应性 将要研究的中间体包括卡宾（二价 碳物种）、氮烯（单价氮物种），以及 有机金属中间体具有16个电子，而不是 金属原子周围稳定的18电子互补。铁，锇， 和钌金属原子将被纳入 有机金属中间体

The mechanistic basis underlying intramolecular hydrogen migration reactions in reactive organic and organometallic intermediates will be studied. Low-temperature matrix isolation spectroscopy, low- temperature NMR spectroscopy, and time-resolved absorption spectroscopy will be used to establish rearrangement pathways and to characterize the reactive species. Organic carbenes, organic nitrenes, and certain coordinately unsaturated 16-electron organometallic intermediates comprise an isolobal class of electron-deficient reactive intermediates that will be studied. In the organometallic studies, low-temperature NMR will be used to follow the chemistry of reactive allyl hydride intermediates and the involvement of these species in alkene isomerization processes. Iron, Osmium, and Ruthenium metal atoms will be incorporated in the organometallic intermediates. In particular, studies will be directed to allylic C-H and beta C-H insertion reactions. In the organic studies, experiments will focus on direct observation of hydrogen migration reactions of carbenes and 1,4-biradicals by time-resolved spectroscopy. %%% This grant from the Organic Dynamics Program supports the work of Professor Robert J. McMahon at the University of Wisconsin. The details of how hydrogen atoms migrate in reactive electron- deficient organic and organometallic intermediates by intramolecular processes will be studied. These elusive intermediates will be studied at low temperatures by various spectroscopic methods in order to characterize the intermediates and individual steps in the overall reaction. The reactive intermediates that will be studied include carbenes (divalent carbon species), nitrenes (monovalent nitrogen species), and organometallic intermediates that have 16 electrons rather than the stable 18-electron complement about the metal atom. Iron, Osmium, and Ruthenium metal atoms will be incorporated in the organometallic intermediates.