Reactive Intermediates and Reaction Mechanisms

反应的基本动力学，包括形成和 随后不稳定化学物质的反应性， 将探测多自由基和两性离子。并发 ESR、NMR和光学瞬态光谱学的使用将 提供基本的机械信息， 设计高活性化学反应 从理性的角度来看。研究课题为 研究的主要内容包括：（1）通过 二甲基富烯及相关试剂;（2）生产 不相交的双自由基;（3）自旋的确认 四亚甲基苯的多重性和反应性;（4） 双自由基多重带隙的调整， 不连续四亚甲基乙烷;（5）多自由基的合成 基于两个二亚甲基杂环通过 （6）稳定的三聚氰胺的合成与表征 双自由基这些化学系统将作为 具有光学、导电和磁性的材料， 实际重要性。 %%% 有机动力学计划的这笔赠款支持 杰罗姆A.耶鲁大学的贝尔森 大学贝尔森教授和他的研究小组将探索 非常活泼的物种，称为双自由基，形成于 化学过程的中间阶段， 只有十亿分之几秒关于这些的信息 中间体可能使设计全新的分子成为可能 具有重要的化学和技术特性。的概念 从这项工作中得出的结论对于理解 分子如何导电和与光相互作用的理论 也将有助于化学系统的设计， 用于制造光纤，以在 光脉冲的形式更快，更有效地长时间 的距离.

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.