Abstract
Two new tripodal heptadentate ligands, tris{2-[2-(1-methyl)imidazolyl]methyliminoethyl}amine ((mim) 3tren) and tris{2-[2-(1-methyl)imidazolyl]methylaminoethyl}amine ((mim) 3htren), containing polyimidazole groups were synthesized. Three corresponding metal complexes [Fe(mim) 3tren](PF 6) 2 ( 1) [Mn(mim) 3tren](ClO 4) 2·MeCN ( 2) and [Mn(mim) 3htren](ClO 4) 2 ( 3) were prepared and characterized by X-ray crystallography. The metal atoms in 1 and 2, being in distorted [MN 6] octahedra, are coordinated by the three imine nitrogen atoms and the three imidazole nitrogen atoms with M–N bond distances of 2.180(4)–2.260(4) and 2.268(3)–2.312(3) Å for 1 and 2, respectively. In 3, the Mn(II) atom is hepta-coordinated by seven nitrogen atoms from htren(mim) 3 to form a monocapped anti-trigonal prism with the Mn–N imine, Mn–N imine and Mn–N tripodal bonds having lengths of 2.235(7), 2.369(6) and 2.507(10) Å, respectively. The reactivities of the complexes with superoxide have been investigated by UV–Vis and electrochemical methods, showing that a new species symbolized as a [Fe–O 2 n− ] or [Mn–O 2 n− ] adduct was formed and that these complexes are effective superoxide scavengers.
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