Experimental data concerning reactions of the bromine atoms with haloalkanes and carbonyl compounds (25 reactions) have been analyzed within the intersecting parabolas model. The following factors have an effect on the activation energy of these reactions: enthalpy of reaction, triplet repulsion, electronegativity of reaction center atoms, dipole–dipole and multidipole interactions of the reaction center with polar groups, and the interaction of π electrons with electrons of the reaction center. The increments characterizing the contribution from each factor to the activation energy of the reaction have been calculated. The increment ΔEμ, which characterizes the dipole–dipole interaction in the transition state, and the dipole moment of the polar group (μ) are correlated by the following empirical equation: ln(ΔE μ/Σμ) = −0.14 + 0.47(ΔE μ/Σμ) − 0.024(ΔE μ/Σμ)2.
Kinetics and Catalysis – Springer Journals
Published: Aug 2, 2017
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