Abstract
A structure-reactivity correlation for the reaction (HO• + HCR3 → HOH + CR3•) has been formulated: log k298(per H) = − 0.000630 ΔrH2 − 0.151 ΔrH − 1.056 ΣF – 1.053 ΣR – 21.26 (r2 = 0.885; n = 70; mean unsigned deviation = 0.29 log units), where ΔrH is the reaction enthalpy and F and R represent the dissection of Hammett’s σpara constant into its field/inductive and resonance effects, and compared for the analogous case for Cl• (ref 1). Although more exothermic, the dependence of HO• on ΔrH is somewhat greater than Cl•. However the dependence on F and R is much less, suggestive of less charge separation in the transition state for the less electronegative HO•. The range of k(OH) is significantly less than that of Cl•, i.e., it is less dependent on substrate structure. Yet a cross-over exists such that k(Cl) > k(HO) predominates for more reactive cases whereas k(Cl) < k(OH) characterizes the less reactive. The Arrhenius parameters reveal that this cross-over results from a change in {E(Cl) − E(OH)} from negative to positive. In contrast, whereas the A factors for both increase significantly as reactivity increases, {A(Cl) / A(OH)} always exceeds unity.