Metal-and Ligand-Centered Monoelectronic Oxidation of #mu#-Nitrido[((tetraphenylporphyrinato)manganese)(phthalocyaninatorn)],[(TPP)Mn-N-FePc]. X-ray Crystal Structure of the Fe(IV)-Containing Species [(THF)(TPP)Mn-N-FePc(H_2O)](I_5)centre dot2THF

摘要

The reaction of #mu# nitrido[((tetraphenylporphyrinato)manganese)(phthalocyaninatoiron)], [(TPP)Mn-N-FePc], with I_2 in THF develops with the formation of two different species, i.e.,[(THF)(TPP)Mn-N-FePc(H_2O)](I_5)centre dot 2THF(I) and [(TPP)Mn~TV-N-Fe~IIIPc](I_3)(II). On the basis of single-crystal X-ray work and Mossbauer, 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 Mn~IV-N-Fe~III=N=Fe~TV system (metal-centered oxidation). Data at hand for II(Mossbauer, EPR, Raman) show, instead, that oxidation takes place at one of the two macrocycles, very likely TPP (Mossbauer, EPR,Raman) show, instead, that oxidation takes place at one of the two macrocycles, very likely TPP (ligand-centered oxidation). The same catiomic fragment present in I, and comtaining the Mn~IV=N=Fe~TV bond system, is also lbtained when (TPP)Mn-N-FePc is allowed to react in THF with (phen)SbCl_6(molar ratio 1:1). There are indications that the use of (phen)SbCl_6 in excess (2:1 molar ratio), in benzene, probably determines further oxidation with the formation of a species showing the combined presence of the Mn~IV-Fe~IV couple and of a #pi#-cation radical.