Reactive Intermediates and Reaction Mechanisms

反应中间体和反应机理

• 批准号: 9119957
• 负责人: Jerome Berson
• 金额: $ 59.37万
• 依托单位: Yale 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: 1992-02-01 至 1996-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9119957&HistoricalAwards=false
• 关键词: Reactive; Intermediates; Reaction; Mechanisms; Reactive; Intermediates; Reaction; Mechanisms

The basic kinetics of reactions which involve the formation and subsequent reactivity of unstable chemical species such as multiradicals and zwitterions will be probed. The concurrent use of ESR, NMR, and optical transient spectroscopy will provide basic mechanistic information which will aid in designing chemical reactions involving highly reactive intermediates from a rational viewpoint. The research topics to be investigated include: (1) the trapping of oxyallyls via dimethylfulvene and related agents; (2) production of disjointed biradicals; (3) confirmation of the spin multiplicity and reactivity of tetramethylene benzene; (4) adjustment of the multiplet gap of biradicals based upon disjointed tetramethyleneethanes; (5) synthesis of polyradicals based upon coupling of two dimethyleneheterocycles via a benzene ring; and (6) synthesis and characterization of stable biradicals. These chemical systems will serve as models for materials with optical, conducting, and magnetic properties of practical importance. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Jerome A. Berson at Yale University. Professor Berson and his research group will probe very reactive species, called diradicals, which are formed in the intermediate stages of chemical processes and often live for only a few billionths of a second. Information about these intermediates may make it possible design totally new molecules with important chemical and technical properties. The concepts to be derived from this work are critical to the understanding of how molecules conduct electricity and interact with light, and will also aid in the design of chemical systems which can be used to make optical fibers to transmit information in the form of light pulses faster and more efficiently over long distances.

将探测涉及不稳定化学物种（如多自由基和z连挥发性物质）的反应的基本动力学。 ESR，NMR和光学瞬态光谱的同时使用将提供基本的机械信息，这将有助于从合理的角度设计涉及高反应性中间体的化学反应。要研究的研究主题包括：（1）通过二甲基饱和剂和相关剂捕获氧气； （2）生产分离的Biradicals； （3）确认四甲基苯的自旋多样性和反应性； （4）根据分离的四甲基乙烷的分离，调整了Biradicals的多重距离； （5）基于通过苯环偶联到两个二甲基乙烯的偶联而合成的； （6）稳定的Biradicals的合成和表征。这些化学系统将用作具有光学，导电和磁性特性的材料的模型。 %% %%来自有机动力学计划的这笔赠款支持耶鲁大学杰罗姆·贝尔森教授的持续工作。贝森教授及其研究小组将探测非常反应性的物种，称为diradicals，这些物种是在化学过程的中间阶段形成的，通常只有几十亿秒的时间。有关这些中间体的信息可能会使具有重要的化学和技术特性的全新分子设计。从这项工作中得出的概念对于理解分子如何传导电和与光相互作用至关重要，并且还将有助于设计化学系统，这些化学系统可用于使光纤以光脉冲的形式更快，更有效地在长距离上传输信息。