The reaction of mu -nitrod[((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(H2O)](I-5). 2THF (I) and [(TPP)Mn-IV-N-(FePc)-Pc-III](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-IV 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 (ligand-centered oxidation). The same cationic fragment present in I, and containing the Mn-IV=N=Fe-IV 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 Mn-IV-Fe-IV couple and of a pi -cation radical.

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 / M. P., Donzello; C., Ercolani; U., Russo; A., CHIESI VILLA; Rizzoli, Corrado. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 40:(2001), pp. 2963-2967. [10.1021/ic000874m]

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

RIZZOLI, Corrado
2001-01-01

Abstract

The reaction of mu -nitrod[((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(H2O)](I-5). 2THF (I) and [(TPP)Mn-IV-N-(FePc)-Pc-III](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-IV 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 (ligand-centered oxidation). The same cationic fragment present in I, and containing the Mn-IV=N=Fe-IV 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 Mn-IV-Fe-IV couple and of a pi -cation radical.
2001
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 / M. P., Donzello; C., Ercolani; U., Russo; A., CHIESI VILLA; Rizzoli, Corrado. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 40:(2001), pp. 2963-2967. [10.1021/ic000874m]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/1460848
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