Chemically Triggered C-ON Bond Homolysis in Alkoxyamines. Part 2: DFT Investigation and Application of the pH Effect on NMP

In recent work, a 15‐fold increase in the C–ON bond homolysis rate constant kd of 4‐pyridylethyl‐SG1‐based alkoxyamine was observed upon protonation of the pyridyl moiety in organic solvent. In this report, the pH dependence of kd (pKa = 4.7) is investigated in D2O/CD3OD (v/v 1:1). A 64‐fold increase in kd is observed at acidic pH. Calculations show that the increase in kd upon protonation is due to both an increase in the stabilization of the protonated 4‐pyridylethyl radical and an increase of the destabilization of the starting materials through an increase in the polarity of the alkyl fragment. This new alkoxyamine is applied to NMP of styrene and sodium styrene sulfonate. The pH effect on the C—ON bond homolysis of activable alkoxyamines is highlighted by a 64‐fold increased in kd from pH 6.7 (1) to pH 3.0 (1H+). The effect of pH is investigated for the NMP of styrene and sodium styrene sulfonate.