Investigation of Reactive Intermediates: 1,1 and 1,4 Biradicals and Cation Radicals

反应中间体的研究：1,1 和 1,4 双自由基和阳离子自由基

• 批准号: 9312429
• 负责人: Joshua Goodman
• 金额: $ 23.4万
• 依托单位: University of Rochester
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-07-01 至 1997-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9312429&HistoricalAwards=false
• 关键词: Investigation; Reactive; Intermediates; Biradicals; Cation

Several chemical reactions which involve highly reactive, short-lived intermediates will be examined. The role of these intermediates will be probed with time-resolved absorption spectroscopy and photoacoustic calorimetry. Two major goals will be pursued. First, these techniques will be applied to reactive intermediates which include 1,1- and 1,4-biradicals and their oxidation products, 1,1- and 1,4- biradical cations. Second, the results will be used to understand what factors are important in determining how these intermediates are converted to products. Factors such as substitution, temperature, method of generation, and solvent will be considered, which will provide insight into how structure and thermodynamics affect their reactivity. %%% This grant from the Organic Dynamics Program supports the continuing work of Joshua L. Goodman at the University of Rochester. Key reactive intermediates in organic chemistry will be studied that have two formal bonds to carbon (carbenes or 1,1-biradicals) and three formal bonds (1,4- biradicals). In the latter instance, two such carbon centers are found in an intermediate. These intermediates will be probed by spectroscopic and calorimetric means on a short time-scale. The results will provide an understanding as to what factors determine the products from these intermediates.

几种化学反应涉及高活性， 将检查短寿命的中间体。的作用 这些中间体将用时间分辨的 吸收光谱和光声量热法。两 将追求主要目标。首先，这些技术将 应用于包括1，1-和 1，4-双自由基及其氧化产物，1，1-和1，4- 双自由基阳离子第二，结果将用于 了解哪些因素在决定 这些中间体转化为产物。等因素 作为替代，温度，生成方法，以及 溶剂将被考虑，这将提供深入了解 结构和热力学如何影响它们的反应性。 %%% 有机动力学计划的这笔赠款支持 约书亚L.古德曼在密歇根大学 罗切斯特。有机化学中的关键活性中间体 将被研究，有两个正式的碳键， （卡宾或1，1-双自由基）和三个形式键（1，4- 双自由基）。在后一种情况下，两个这样的碳中心 存在于中间体中。这些中间体将 通过光谱和量热方法在短时间内探测 时间尺度结果将提供一个理解， 是什么因素决定了这些产品 中间体的