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

我们将研究几种涉及高活性、短寿命中间体的化学反应。这些中间体的作用将用时间分辨吸收光谱和光声量热法来探测。将追求两个主要目标。首先，这些技术将应用于反应中间体，包括1,1-和1,4-双基及其氧化产物，1,1-和1,4-双基阳离子。其次，研究结果将用于了解哪些因素在决定这些中间体如何转化为产品方面是重要的。取代、温度、生成方法和溶剂等因素将被考虑，这将为结构和热力学如何影响它们的反应性提供见解。这项来自有机动力学项目的资助将支持罗切斯特大学Joshua L. Goodman的持续工作。有机化学中的关键反应中间体将研究与碳有两个形式键（碳烯或1,1-双基）和三个形式键（1,4-双基）。在后一种情况下，在中间体中发现两个这样的碳中心。这些中间体将在短时间内通过光谱和量热方法进行探测。结果将提供一个了解是什么因素决定这些中间体的产品。

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.