Abstract: | The iron(III) complexes of the tripodal benzimidazole‐containing ligands tris(2‐benzimidazolylmethyl)amine (ntb), bis(2‐benzimidazolylmethyl)(2‐hydroxyethyl)‐amine (bbimae) and tris(5,6‐dimethyl‐2‐benzimidazolylmethyl)amine (me2ntb) are structural and functional models for intradiol cleaving catechol dioxygenases. The complexes Fe(ntb)Cl2]Cl · 3 CH3OH ( 1 ; P 1, a = 9.830(2) Å, b = 12.542(3) Å, c = 13.139(3) Å, α = 82.88(3)°, β = 73.45(3)°, γ = 85.53(3)°, V = 1539.2(6) Å3; Z = 2) and Fe(bbimae)Cl2]Cl ( 2 ; P21/n, a = 7.461(2) Å, b = 18.994(5) Å, c = 14.515(4) Å, β = 98.22(2)°, V = 2035.8(9) Å3, Z = 4) have been characterized by X‐ray crystallography and spectroscopic methods. In the octahedrally coordinated complexes two cis coordination sites – essential for catechol binding – are occupied by chloride ligands. The significant intradiol cleaving catechol dioxygenase activity of the model complexes was examined using 3,5‐di‐tert‐butylcatechol as a substrate. |