Absolute rate calculations for atom abstractions by radicals: energetic, structural and electronic factors.
We calculate transition-state energies of atom-transfer reactions from reaction energies, electrophilicity indices, bond lengths, and vibration frequencies of the reactive bonds. Our calculations do not involve adjustable parameters and uncover new patterns of reactivity. The generality of our model is demonstrated comparing the vibrationally adiabatic barriers obtained for 100 hydrogen-atom transfers with the corresponding experimental activation energies, after correction for the heat capacities of reactants and transition state. The rates of half of these reactions are calculated using the Transition-State Theory with the vibrationally adiabatic path of the Intersecting-State Model and the semiclassical correction for tunneling (ISM/scTST). The calculated rates are within an order of magnitude of the experimental ones at room temperature. The temperature dependencies and kinetic isotope effects of selected systems are also in good agreement with the available experimental data. Our model elucidates the roles of the reaction energy, electrophilicity, structural parameters, and tunneling in the reactivity of these systems and can be applied to make quantitative predictions for new systems.
Arnaut
Luis G
LG
Universidade de Coimbra, Departamento de Química, P-3049 Coimbra Codex, Portugal. lgarnaut@ci.uc.pt
Pais
Alberto A C C
AA
Formosinho
Sebastião J
SJ
Barroso
Monica
M