C–ON bond homolysis of alkoxyamines: when too high polarity is detrimental

Abstract

Throughout the last decade, the effect of electron withdrawing groups (EWGs) has been known to play a role – minor or moderate depending on the nitroxyl fragment R₁R₂NO – in the change in the homolysis rate constant (k_d) for C–ON bond homolysis in alkoxyamines (R₁R₂NOR). It has been shown that the effect of EWGs on k_d is described by a linear relationship with the electrical Hammett constant σ_I. Since then, linear multi-parameter relationships f(σ_RS,ν,σ_I) have been developed to account for the effects involved in the changes in k_d, which are the stabilization of the released radical (σ_RS) and the bulkiness (ν) and polarity (σ_I) of the alkyl fragment. Since a decade ago, new results have been published highlighting the limits of such correlations. In this article, previous multi-parameter linear relationships are amended using a parabolic model, i.e. (σ_I,nitroxide − σ_I,alkyl)², to describe the effect of EWGs in the alkyl fragment on k_d. In contrast to previous studies, these improved linear multi-parameter relationships f(σ_RS,ν,Δσ_I²) are able to account for the presence of several EWGs on the alkyl fragment, R. An unexpectedly strong solvent effect – a ca. 1500-fold increase in k_d – from tert-butylbenzene to the water/methanol mixture is also observed for 3-((2,2,6,6-tetramethylpiperidin-1-yl)oxyl)pentane-2,4-dione 1b in comparison to a ca. 5-fold increase in k_d that is generally observed.