Comparison of the SOD-like activity of hexacoordinate Mn(II), Fe(II) and Ni(II) complexes having isoindoline-based ligands

Recently, a series of Fe(II) complexes have been published by our group with 3 N-donor 1,3-bis(2′-Ar-imino)isoindoline ligands containing various Ar-groups (pyridyl, 4-methylpyridyl, thiazolyl, benzimidazolyl and N-methylbenzimidazolyl). The superoxide scavenging activity of the compounds showed correlation with the Fe(III)/Fe(II) redox potentials. Analogous, electroneutral chelate complexes with Mn(II) and Ni(II) in 2:1 ligand:metal composition are reported here. Each Mn(II) complex exhibits one reversible redox wave that is assigned as the Mn(III)/Mn(II) redox transition. The E1/2 spans a 180 mV range from − 98 (Ar = 3-methylpyridyl) to 82 mV (Ar = thiazolyl) vs. the Fc+/Fc depending on the Ar-sidearm. The SOD-like (SOD=superoxide dismutase)activity of all complexes was determined according to the McCord–Fridovich method. The Mn(II) isoindolinates have IC50 values – determined with 50 μM cytochrome c Fe(III) – that range from (3.22 ± 0.39) × 10− 6 (Ar = benzimidazolyl) to (10.80 ± 0.54) × 10− 6 M (Ar = N-methylbenzimidazolyl). In contrast with the Fe(II) complexes, the IC50 concentrations show no significant dependence on the E1/2 values in this narrow potential range emphasizing that the redox potential is not the governing factor in the Mn(II)-containing scavengers. The analogous Ni(II) compounds show no redox transitions in the thermodynamically relevant potential range (− 0.40 to 0.65 V vs. SCE) and accordingly, their superoxide scavenging activity (if any) is below the detection level.

Graphical AbstractMononuclear complexes of three different metal ions (Mn(II), Fe(II) and Ni(II)) with isoindoline-based ligands show diverse redox behavior and versatile structural distortions. Comparison of their superoxide scavenging activities establishes the following order: Fe ≥ Mn>>>Ni. Beside the metal centered redox potential, functional groups on the ligands seem to affect the reactivity towards superoxide.Figure optionsDownload as PowerPoint slide