Mononuclear iron(ii) complexes containing a tripodal and macrocyclic nitrogen ligand: synthesis, reactivity and...

Two novel tripodal ligands L¹ and L² based on a tris(methylpyridyl)amine (TPA) motif have been prepared and reacted with two different iron(ii) salts. The ligand L¹ contains a bis(amino-phenyl)-TPA group whereas the macrocyclic ligand L² displays two different coordinating cores, namely TPA and pyridine-dicarboxamide. The resulting mononuclear complexes 1-4 have been characterized in the solid state and in solution by spectroscopic and electrochemical methods. All complexes are high spin and mainly pentacoordinated. X-ray diffraction analyses of the crystals of complexes 2 and 3 demonstrate that the coordination sphere of the iron(ii) centre adopts either a distorted bipyramidal-trigonal or square pyramidal geometry. In the absence of an exogenous substrate, oxidation of complex 2 by H₂O₂ induces an intramolecular aromatic hydroxylation, as shown by the X-ray structure of the resulting dinuclear complex 2'. Catalytic studies in the presence of a substrate (cyclohexane) show that the reaction process is strongly impacted by the macrocyclic topology of the ligand and the nature of the counter-ion.