Photolysis of CpFe(ρ-xylene)+ (Cp = η5-cyclopentadienyl) in the presence of suitable 6- or 2-electron donor ligands results in replacement of the aromatic ring with one 6-electron or three 2-electron donor ligands. The compounds [CPFe(η6-C7H8)]BF4 (C7H8 = cycloheptatriene), [CpFe(η6-C8H8)]PF6, (C8H8 = cyclooctatetraene), [CpFe(η6-PCP)]PF6 (PCP = 2,2-paracyclophane), [CpFe-(P(OCH3)3)3]PF6 and [CpFe(P(OCH2CH3)3)3]PF6 were prepared in this manner. The compound [CpFe(TM4)3FeCp](PF6)2 · CH3COCH3 (TM4 = 2,5-dimethyl-2,5 diisocyanohexane) was prepared in two steps. First, [CpFe(ρ-xylene)]PF6 was irradiated with an excess of the free TM4 ligand producing a mixture of [CpFe(TM4)3]+ and [CpFe(TM4)3FeCp]2+. An additional equivalent of [CpFe(p-xylene)]PF6 was added to this mixture and photolysis yielded [CpFe(TM4)3FeCp](PF6)2 · CH3COCH3.