Intermediate-Spin (S=3/2) Porphyrinato-iron(III) Complexes
David DolphinH., Sams, J.R., and Tsin, T.B.
Octaethylporphyrinatoiron(III) chloride, Fe(Z)Cl, in CH2Cl2 was shaken with aqueous 2M NaOH to give dimeric μ-oxobis[octaethylporphyrinatoiron(III)], which, in CH2Cl2 was treated with aqueous 2M HClO4, then EtOH, to give Fe(Z)ClO 4.2EtOH (I). Heating I in vacuo at 60oC for 6 hr gave Fe(Z)ClO4. Both complexes have S = 3/2 ground states. Effective magnetic moments and Moessbauer quadrupole splittings offer conclusive evidence for the S = 3/2 assignment. Moessbauer and ir spectra suggest that the Fe atom in Fe(Z)ClO4 is probably pentacoordinate and in I is probably hexacoordinate.