Heterospin MnIII complex as a reaction product of the redox-induced change in the ligand coordination mode

The reaction of Mn^II chloride with imino nitroxide radical, 2-(2-hydroxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl (HL²), affords the Mn^III complex [MnL² ₂L³]·Me₂CO, a distinctive feature of which is the simultaneous presence in the ligand shell of both the initial imino nitroxide and the product of its reduction 2-(2-hydroxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide (HL³). The reaction involves the oxidation of Mn^II to Mn^III and the reduction of the imino nitroxide radical to the corresponding amidine oxide along with a change in the coordination mode of the heterocyclic ligand on going from L² to L³. The Mn^III ion forms with L² six-membered metallocycles typical of Schiff bases, whereas with L³ Mn^III forms a seven-membered metallocycle due to the coordination of L³ by oxygen atoms of the phenol and N-oxide It was found in a similar reaction of Ni^II chloride with imino nitroxide HL² that no oxidation of the metal occurred and bis(chelate) [NiL² ₂(H₂O)₂]·2Me₂CO was formed in the solid phase. The molecular and crystal structures of the compounds were determined, and their magnetic properties were studied.