With the use of the model complexes [(PQ)FeCl(CH3O)](+), [(phen)FeCl(CH3O)](+), and [(PQ)(phen)FeCl(CH3O)](+), where PQ is 9,10-phenanthraquinone and phen is 1,10-phenanthroline, the reactivity of phenanthraquinone in complexes with iron(III) is investigated. It is shown that 9,10-phenanthraquinone takes part in redox processes occurring at iron and thereby allows the oxidation of methanolate to formaldehyde. The oxidation is driven by the reduction of iron(III) to iron(II) and 9,10-phenanthraquinone to the semihydroquinone radical or semiquinolate, if the hydrogen atom is transferred from methanolate to chlorine rather than PQ. 1,10-Phenanthroline, on the other hand, acts as an innocent ligand, and the [(phen)FeCl(CH3O)](+) complex shows a typical two-state reactivity. The reactivity of [(PQ)(phen)FeCl(CH3O)](+) reveals that the hexacoordination of iron energetically facilitates the oxidation of methanolate, and therefore it is proposed that, in the presence of suitable reductants, the mixture of iron(III) and 9,10-phenanthraquinone can lead to the generation of the semihydroquinone radicals, species responsible for the toxicity of PQ. The fragmentation of [(PQ)(phen)FeCl(CH3O)](+) also demonstrates a strong binding of phen toward iron(III), which is a reason for using phen as an iron chelator in biochemistry. The structures and reactivities of the complexes are investigated by means of mass spectrometry, infrared multiphoton dissociation spectra, and density functional theory calculations.