Catalase vs Peroxidase Activity of a Manganese(II) Compound: Identification of a Mn(III)―(μ-O)2―Mn(IV) Reaction Intermediate by Electrospray Ionization Mass Spectrometry and Electron Paramagnetic Resonance Spectroscopy

Herein, we report reactivity studies of the mononuclear water-soluble complex [Mn(II)(HPClNOL)(η1-NO3)(η2-NO3)] 1, where HPClNOL = 1-(bis-pyridin-2-ylmethyl-amino)-3-chloropropan-2-ol, toward peroxides (H2O2 and tert-butylhydroperoxide). Both the catalase (in aqueous solution) and peroxidase (in CH3CN) activities of 1 were evaluated using a range of techniques including electronic absorption spectroscopy, volumetry (kinetic studies), pH monitoring during H2O2 disproportionation, electron paramagnetic resonance (EPR), electrospray ionization mass spectrometry in the positive ion mode [ESI(+)-MS], and gas chromatography (GC). Electrochemical studies showed that 1 can be oxidized to Mn(III) and Mn(IV). The catalase-like activity of 1 was evaluated with and without pH control. The results show that the pH decreases when the reaction is performed in unbuffered media. Furthermore, the activity of 1 is greater in buffered than in unbuffered media, demonstrating that pH influences the activity of 1 toward H2O2. F...