Chemical and Spectroscopic Studies of Radical Cation Reactivity and Structures

自由基阳离子反应性和结构的化学和光谱研究

• 批准号: 9110487
• 负责人: Heinz Roth
• 金额: $ 25.2万
• 依托单位: Rutgers University New Brunswick
• 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: 1991-06-15 至 1994-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9110487&HistoricalAwards=false
• 关键词: Chemical; Spectroscopic; Studies; Radical; Cation

The structures and reactions of unusual radical cations will be investigated. A variety of organic radical cations will be generated in a range of media, including fluid solutions, frozen glasses, and solid supports, e.g., zeolites, by appropriate methods, including photo-induced electron transfer, chemical oxidation, and radiolysis. Their structures and reactions will be examined by a variety of modern spectroscopic methods, including steady-state and time-resolved optical and electron spin resonance spectroscopy. In addition, CIDNP and two-photon (radical cation photochemistry) will be used to monitor these reactions. The intermediates will be probed by a range of reagents designed to intercept the unpaired spin (free radical addition), the charge (nucleophilic capture), or both functions (cycloaddition of superoxide or semiquinone anion). The influence of surface interactions and external constraints on the three-dimensional structures of radical cations and their rearrangements will be probed by adsorbing the substrate on the microscopic surfaces of solid supports or sequestering in the three-dimensional enclaves of zeolites. %%% This grant from the Organic Dynamics Program supports the work of Professor Heinz D. Roth at Rutgers University. Radical cations are derived from neutral molecules by the loss of an electron to give a reactive intermediate with one unit of positive charge and one unpaired electron. Electrons in stable molecules are paired, while the reactive intermediates with unpaired electrons are referred to as free radicals. In this research, structures of unusual radical cations will be determined by modern instrumental methods and the reactions of these intermediates will be studied as well. Various chemical reactions will be used to intercept these reactive intermediates, and thereby determine their structures. The influence of surface interactions and external constraints on the reactions of these radical cations will also be investigated.

不寻常的自由基阳离子的结构和反应将是 研究了各种有机自由基阳离子将被 在一系列介质中产生，包括液体溶液、冷冻 玻璃和固体载体，例如，沸石，通过适当的 方法，包括光诱导电子转移，化学 氧化和辐解。它们的结构和反应 通过各种现代光谱方法进行检查，包括 稳态和时间分辨光学和电子自旋共振 谱此外，CIDNP和双光子（自由基阳离子 光化学）将用于监测这些反应。的 中间体将被一系列试剂探测， 拦截不成对的自旋（自由基加成）， （亲核捕获）或两种功能（亲核捕获的环加成）。 超氧化物或半醌阴离子）。表面的影响 相互作用和外部约束的三维 自由基阳离子的结构及其重排将是 通过将底物吸附在 固体支持物或隔离在三维包体中 沸石。 %%% 有机动力学计划的这笔赠款支持以下工作： 海因茨教授D.罗格斯大学的罗斯。自由基阳离子是 从中性分子中通过失去一个电子而得到 一种活性中间体，带有一个正电荷单位和一个 稳定分子中的电子是成对的， 具有不成对电子的反应性中间体被称为 作为自由基。在这项研究中，不寻常的自由基的结构， 阳离子将通过现代仪器方法测定， 也将研究这些中间体的反应。各种 化学反应将被用来拦截这些反应性的 中间体，从而确定其结构。的 表面相互作用和外部约束的影响 还将研究这些自由基阳离子的反应。