| Résumé | A general cycle was developed that defines the thermodynamics for all of the homolytic and heterolytic cleavage reactions of a hydrocarbon, R-R’, in solution. Only seven experimental parameters were needed in order to define the energetics for all 11 of the possible cleavage reactions of R-R’. These parameters were the oxidation and reduction potentials of R-R’, R’, and R” and the homolytic, R-R’, bond energy. The utility of this approach was demonstrated for the case where R was an arylmethyl group and R’ was hydrogen. The oxidation and reduction potentials of the arylmethyl radicals were measured by modulation voltammetry in acetonitrile, and the homolytic C-H bond energies of the corresponding hydrocarbons were measured by photoacoustic calorimetry. The cycle was also extended to a case where R-R’ was a radical rather than a closed-shell molecule. |
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