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

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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.