The mixed-ligand bimetallic N-bridged, formally mixed-valence Fe(II1)-Fe(1V) species (TPP)Fe-N-FePc, previously reported, and the heterobimetallic analogue (TPP)Fe-N-RuPc have been prepared and characterized, and their redox properties have been examined. Oxidation of these species with I2 leads in both cases to monopositively charged Fe-Fe and Fe-Ru mu-nitrido dimers, having I5- as counterion. By reaction with NaBH4, these salt-like species are reduced to the starting materials. The structure of the complex [(THF)(TPP)Fe-N- FePc(H20)](I5).2THF has been elucidated by an X-ray study. The complex crystallizes in the monoclinic system. Unit cell data: formula C88H70Fe2IsN1304, M = 2119.94, a = 27.13(1) A°, b=12.032(5) A°, c = 25.596(41) A°, V = 8298(20) A°3, Z = 4, space group Cc. The structure shows that the phthalocyanine and tetraphenylporphyrin rings are held together by the nearly linear triatomic Fe-N-Fe moiety (179°). Each Fe atom within the molecule lies in the plane of the respective macrocycle, six-coordination being achieved by external axial ligation of H20 and THF molecules at the PcFe and (TPP)Fe sites, respectively. The H20 molecule is hydrogen-bonded to two additional THF molecules. The I5- ion is V-shaped and lies separately in the crystal. Additional information on the molecular and electronic structure of the present Fe-Fe and Fe-Ru species has been obtained from IR, Raman, Mossbauer, and EPR spectra and also from magnetic susceptibility data.
(.mu.-Nitrido)((tetraphenylporphyrinato)iron)((phthalocyaninato)iron) and Its Fe-Ru Analog: Redox Behavior and Characterization of New Fe(IV)-Containing Species. X-ray Crystal Structure of [(THF)(TPP)Fe-N-FePc(H2O)](I5).cntdot.2THF
G Pennesi;
1995
Abstract
The mixed-ligand bimetallic N-bridged, formally mixed-valence Fe(II1)-Fe(1V) species (TPP)Fe-N-FePc, previously reported, and the heterobimetallic analogue (TPP)Fe-N-RuPc have been prepared and characterized, and their redox properties have been examined. Oxidation of these species with I2 leads in both cases to monopositively charged Fe-Fe and Fe-Ru mu-nitrido dimers, having I5- as counterion. By reaction with NaBH4, these salt-like species are reduced to the starting materials. The structure of the complex [(THF)(TPP)Fe-N- FePc(H20)](I5).2THF has been elucidated by an X-ray study. The complex crystallizes in the monoclinic system. Unit cell data: formula C88H70Fe2IsN1304, M = 2119.94, a = 27.13(1) A°, b=12.032(5) A°, c = 25.596(41) A°, V = 8298(20) A°3, Z = 4, space group Cc. The structure shows that the phthalocyanine and tetraphenylporphyrin rings are held together by the nearly linear triatomic Fe-N-Fe moiety (179°). Each Fe atom within the molecule lies in the plane of the respective macrocycle, six-coordination being achieved by external axial ligation of H20 and THF molecules at the PcFe and (TPP)Fe sites, respectively. The H20 molecule is hydrogen-bonded to two additional THF molecules. The I5- ion is V-shaped and lies separately in the crystal. Additional information on the molecular and electronic structure of the present Fe-Fe and Fe-Ru species has been obtained from IR, Raman, Mossbauer, and EPR spectra and also from magnetic susceptibility data.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
