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The reaction of μ-oxobis(phthalocyaninatoiron(III)) in pyridine containing small amounts of water has been investigated. The reaction occurs in two consecutive steps. The first step is a disproportionation equilibrium (
K = 1.0×10
−3 mol dm
−3 at 35 °C) yielding [(py)
2Fe(II)(pc)] and the ferryl compound [(py)Fe(IV)(pc)O]. The spectrum of the latter in the 600–700 nm range shows the shape characteristic of phthalocyaninato derivatives with a high intensity Q band (
ϵ = 7.5 × 10
4) at 670 nm. During the succedding step, that requires several hours to be completed, the FeO oxygen is transferred to peripheral sites of the macrocycle, very likely to form C-OH groups. This fact does not modify appreciably the electronic properties of the complex, if compared to those of [(py)
2Fe(pc)], and can be revealed only by FAB experiments which show the presence of phthalocyaninato derivatives of mass 568 + 16 and 568 + 32 (568 being the mass of the molecular ion [Fe(pc)
+]. The first step of this reaction representes a convenient method for preparing pyridine solutions of the ferrylic species, suitable for reactivity studies.