Abstract
To develop an understanding of the reactivity of biradicals and carbenes, it is essential that the energetics of the reactants, intermediates, and products be established. The most successful approach to date for determining the energetics of intermediates, such as radicals, biradicals, and carbenes, has been to estimate their energies through a combination of Benson group additivities(1) and bond enthalpy data.(2) Regrettably, this data base is not sufficiently extensive to allow for the calculation of the energetics for most intermediates of interest. For example, little is known regarding the enthalpic contributions of substituents at a radical center. Also, there is no satisfactory method for estimating the energetics of carbenes and biradicals. Finally, it is not clear how reliable even the best calculation may be for reactive intermediates in the condensed phase as solvent interactions may make significant contributions to the overall energetics. Clearly, it would be advantageous to have experimental methods that could directly probe the energies of transient species.
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Peters, K.S. (1990). Time-Resolved Photoacoustic Calorimetry of Carbenes and Biradicals. In: Platz, M.S. (eds) Kinetics and Spectroscopy of Carbenes and Biradicals. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-3707-0_2
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DOI: https://doi.org/10.1007/978-1-4899-3707-0_2
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