Metal- and Ligand-Centered Monoelectronic Oxidation of μ-Nitrido[((tetraphenylporphyrinato)manganese)(phthalocyaninatoiron)], [(TPP)Mn−N−FePc]. X-ray Crystal Structure of the Fe(IV)-Containing Species [(THF)(TPP)Mn−N−FePc(H2O)](I5)·2THF

The reaction of μ-nitrido[((tetraphenylporphyrinato)manganese)(phthalocyaninatoiron)], [(TPP)Mn−N−FePc], with I2 in THF develops with the formation of two different species, i.e., [(THF)(TPP)Mn−N−FePc(H2O)](I5)·2THF (I) and [(TPP)MnIV−N−FeIIIPc](I3) (II). On the basis of single-crystal X-ray work and Mössbauer, EPR, Raman, and magnetic susceptibility data, I, found to be isostructural with the corresponding Fe−Fe complex, is shown to contain a low-spin triatomic MnIVNFeIV system (metal-centered oxidation). Data at hand for II (Mössbauer, EPR, Raman) show, instead, that oxidation takes place at one of the two macrocycles, very likely TPP (ligand-centered oxidation). The same cationic fragment present in I, and containing the MnIVNFeIV bond system, is also obtained when (TPP)Mn−N−FePc is allowed to react in THF with (phen)SbCl6 (molar ratio 1:1). There are indications that the use of (phen)SbCl6 in excess (2:1 molar ratio), in benzene, probably determines further oxidation with the formation of a species showing the combined presence of the MnIV−FeIV couple and of a π-cation radical.