Iron Complexes Containing Electrochemically Active Diazocycle-bis(di- tert -butyl-phenol) Ligands

Four N, O-donor ligands built on diazocycle platforms and containing bis(di-tert-butyl-phenol) as pendant arms were employed in the synthesis of iron(III) complexes, resulting in four mononuclear and one dinuclear complexes. The ligands are distinct with respect to the diazocycle backbone: piperazine (H2L1), diazepane/homopiperazine (H2L2), hexahydropyrimidine (H2L3) or hexahydropyrimidin-5-ol (H3L4). The molecular structure of compounds [FeL2Cl], 2, and [Fe2(L4)(HL4)Cl], 4, were solved by single crystal X-ray diffraction analysis. Electrochemical data showed that, in addition to the electrochemical process centered on the metal, the compounds show ligand-centered redox processes. Coulometric studies with concomitant UV-Vis analyses confirmed that compound 2 generated the phenoxyl species, while electron paramagnetic resonance (EPR) spectroscopy confirmed the radical formation for compounds 2, 4 and 5. Of interest was the observation that the compound in which the ligand can be oxidized easiest is the one where the metal center shows the lowest Lewis acidity.