Structural effects on the solvolytic reactivity of carboxylic and sulfonic acid chlorides. Comparisons with gas-phase data for cation formation.

@article{Bentley2008StructuralEO,
  title={Structural effects on the solvolytic reactivity of carboxylic and sulfonic acid chlorides. Comparisons with gas-phase data for cation formation.},
  author={Thomas William Bentley},
  journal={The Journal of organic chemistry},
  year={2008},
  volume={73 16},
  pages={6251-7}
}
Kinetic data for solvolyses of 28 acid chlorides in 97% w/w trifluoroethanol (TFE)-water spanning over 10 (9) in rate constant at 25 degrees C are obtained directly or by short extrapolation from published values. G3 calculations of the energy required for cation formation in the gas phase are validated from proton affinities and from other experimental data. G3 calculations of heterolytic bond dissociation enthalpies (HBDEs) for formation of cations from acid chlorides in the gas phase show… CONTINUE READING