Syntheses, structures and properties of a series of non-heme alkoxide-Fe(III) complexes of a benzimidazolyl-rich ligand as models for lipoxygenase

The treatment of Fe(ClO(4))(2)·6H(2)O or Fe(ClO(4))(3)·9H(2)O with a benzimidazolyl-rich ligand, N,N,N',N'-tetrakis(1-methyl-2-benzimidazolyl)methyl]-1,2-ethanediamine (medtb) in alcohol/MeCN gives a mononuclear ferrous complex, Fe(II)(medtb)](ClO(4))(2)·?CH(3)CN·?CH(3)OH (1), and four non-heme alkoxide-iron(III) complexes, Fe(III)(OMe)(medtb)](ClO(4))(2)·H(2)O (2, alcohol = MeOH), Fe(III)(OEt)(Hmedtb)](ClO(4))(3)·CH(3)CN (3, alcohol = EtOH), Fe(III)(O(n)Pr)(Hmedtb)](ClO(4))(3)·(n)PrOH·2CH(3)CN (4, alcohol = n-PrOH), and Fe(III)(O(n)Bu)(Hmedtb)](ClO(4))(3)·3CH(3)CN·H(2)O (5, alcohol = n-BuOH), respectively. The alkoxide-iron(III) complexes all show 1) a Fe(III)-OR center (R = Me, 2; Et, 3; (n)Pr, 4; (n)Bu, 5) with the Fe-O bond distances in the range of 1.781-1.816 ?, and 2) a yellow color and an intense electronic transition around 370 nm. The alkoxide-iron(III) complexes can be reduced by organic compounds with a cis,cis-1,4-diene moiety via the hydrogen atom abstraction reaction.