Unsaturated Hydrocarbon Cation Radical Chemistry

不饱和烃阳离子自由基化学

• 批准号: 8801588
• 负责人: Stephen Nelsen
• 金额: $ 27.02万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-05-01 至 1991-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8801588&HistoricalAwards=false
• 关键词: Unsaturated; Hydrocarbon; Cation; Radical; Chemistry

This grant in Organic and Macromolecular Chemistry provides support for the research of Professor Stephen Nelsen, University of Wisconsin, whose work focuses on the chemistry of organic radical cations. Such species are thought to be important intermediates in a number of oxidation processes. A full understanding of oxidation processes has important practical implications in controlling a variety of oxidations, particularly ones that are destructive to organic molecules. Changes in nuclear and electronic structure upon electron removal from unsaturated hydrocarbon derivatives will be probed by optical and ESR spectroscopy, PE spectroscopy and cyclic voltammetry. Energy differences in the gas phase and in solution between the neutral and ionic state will be determined. Semiempirical calculations will also be carried out. A series of sesquibicyclic alkenes, which will change the amount of pyramidalization which occurs upon electron loss, will be prepared. Comparison of compounds with C=C+. as the formal charge-bearing center with other compounds having the same alkyl groups but NN+. bearing the charge will reveal differences in sigma, pi interactions. Chemistry initiated by irradiation into the sigma, pi transition of these compounds will also be surveyed. Studies of CO bond formation upon chain reaction of dioxygen with these compounds (initiated by their cation radicals) will continue. Unusual selectivities result from the peroxyl-carbocation and peroxide cation radical intermediates, and four, five, and six-membered ring peroxides (dioxetanes, dioxolanes, and endoperoxides), many of which are not available by other methods, have been shown to be formed. Extensions of this Cation Radical Chain Catalyzed (CRCC) chemistry to additions of carbon monoxide, isonitriles, nitrous oxide, and acetylenes will be explored.

有机和高分子化学的这项资助提供了 支持斯蒂芬·尼尔森教授的研究， 威斯康星州大学，其工作重点是化学 有机自由基阳离子 这些物种被认为是 在许多氧化过程中的重要中间体。一 对氧化过程的充分了解对 控制各种氧化的实际意义， 特别是那些对有机分子有破坏性的。 电子后核结构和电子结构的变化 将探索从不饱和烃衍生物中去除 通过光学和ESR光谱，PE光谱和循环 伏安法 气相和气相中的能量差 中性和离子状态之间的溶液将是 测定还将进行半经验计算 出去 一系列的倍半双环烯烃，这将改变 电子损失时发生的电子化量， 会做好准备。 与C = C+的化合物的比较。为 形式电荷承载中心与其他化合物具有 相同的烷基，但NN+。承担指控会暴露 σ和π相互作用的差异。 化学发起人 辐照进入这些化合物的σ，π跃迁 也将被调查。 分子链上CO成键的研究 分子氧与这些化合物的反应（由它们的 阳离子自由基）将继续。 不寻常的选择性结果 来自过氧化碳阳离子和过氧化阳离子自由基 中间体和四元、五元和六元环过氧化物 （二氧杂环丁烷、二氧戊环和内过氧化物），其中许多是 其他方法无法获得的，已经显示出形成。 阳离子自由基链催化的延伸（CRCC） 添加一氧化碳、异腈、亚硝酸的化学 氧化物和乙炔将被探索。