Studies of Olefin Triplets and Triplet Biradicals

烯烃三重态和三重态双自由基的研究

• 批准号: 9422824
• 负责人: Richard Caldwell
• 金额: $ 37.14万
• 依托单位: University of Texas at Dallas
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1995
• 资助国家: 美国
• 起止时间: 1995-03-01 至 1999-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9422824&HistoricalAwards=false
• 关键词: Studies; Olefin; Triplets; Triplet; Biradicals

This renewal award is made in the Organic Dynamics Program in support of the research of Dr. Richard Caldwell. Alkene triplets and triplet biradicals will be studied (1) by conventional organic mechanistic methods to determine chemical outcomes and infer the nature of the intermediates; (2) by laser flash photolysis to determine transient lifetimes and intersystem crossing rates, and energies and kinetic properties of transients, and; (3) by CAS-MCSCF computations of spin-orbit coupling in small model systems. The results will lead to a fundamental understanding of triplet biradicals and olefin triplets, specifically their energetics and energy surfaces, conformations, dynamics, and ultimately the role of all of these in determining the outcomes of photochemical processes. Among the triplet reactions which will be studied are ring-opening rearrangements, olefin addition reactions, and intersystem crossing of olefin triplets. Understanding the fundamental properties and mechanistic behavior of biradical intermediates will provide the chemist with the tools to design new chemical reactions of alkene triplets and extend their role in synthetic photochemistry.

这个更新奖是在有机动力学计划，以支持 理查德考德威尔博士的研究 烯烃三元组和三元组 双自由基将研究（1）通过传统的有机机械 方法来确定化学结果和推断的性质， 中间体;（2）通过激光闪光光解来确定瞬态 寿命和系统间交叉率，能量和动能 瞬态特性，以及（3）通过CAS-MCSCF计算， 小模型系统中的自旋轨道耦合。结果将导致 对三重态双自由基和烯烃三重态的基本理解， 特别是它们的能量和能量表面，构象， 动力学，以及最终所有这些在决定 光化学过程的结果。 在三重态反应中，将研究的是开环反应， 重排，烯烃加成反应，和系统间交叉 烯烃三元组。 了解的基本性质和机械行为， 双自由基中间体将为化学家提供设计 烯烃三重态的新化学反应，并扩展它们在 合成光化学