Tuning the MnII2/MnIII2 redox cycle of a phenoxo-bridged diMn catalase mimic with terminal carboxylate donors

Abstract

A new phenoxo-bridged diMn^III complex, Na[Mn₂L(OH)₂(H₂O)₂]·5H₂O (1), obtained with the ligand L^5- = 5‑methyl‑2‑hydroxo‑1,3‑xylene‑α,α‑diamine‑N,N,N',N'‑tetraacetato, has been prepared and characterized. Mass spectrometry, conductivity, UV-visible, EPR and ¹H NMR spectroscopic studies showed that the complex exists in solution as a monoanionic diMn^III complex. Complex 1 catalyzes H₂O₂ disproportionation with second-order rate constant k_cat = 305(9) M^-1 min^-1 and without a time-lag phase. Based on spectroscopic results, the catalase activity of complex 1 in methanol involves a Mn^III₂/Mn^II₂ redox cycle, which distinguishes this catalyst from other phenoxo-bridged diMn complexes that cycle between Mn^IIMn^III/Mn^IIIMn^IV species. Addition of base stabilizes the catalyst, restrains demetallation during catalysis and causes moderate enhancement of catalase activity. The terminal carboxylate donors of 1 not only contribute as internal bases to assist deprotonation of H₂O₂ but also favor the formation of active homovalent diMn species, just as observed for the enzyme.

Keywords: Catalase mimic; Kinetics; Manganese; Polycarboxylate ligand.