The kinetics and thermochemistry of the gas phase reaction of cyclopentadiene and iodine. Relevance to the heat of formation of cyclopentadienyl iodide and cyclopentadienyl radical
The rate of the reaction of cyclopentadiene with iodine has been followed spectrophotometrically over the temperature range 171.7° to 276.5°C. The reaction first proceeds almost to the point of equilibrium with cyclopentadienyl iodide and HI, although the final products are fulvalene and HI. Equilibrium constants obtained are those predicted by bond additivity. A third-law value of δH0f 298 (c-C5H5I,g) = 49 kcal/mole is obtained. Rate studies of the reaction up to the iodide equilibrium, yield values for the rate constant . Uncertainty in the Arrhenius parameters, as well as doubts as to the applicability of the usual assumption that E3 = 1 ± 1 kcal/mole, make difficult an evaluation of total cyclopentadienyl stabilization energy (TSE) from these data. However, the value is probably 15 < TSE < 20.
