Metallkomplexe mit Tetrapyrrol-Liganden, XIV.

Abstract
An air-stable porphodimethene, namely α, γ-dimethyl-α, γ-dihydrooctaethylporphyrin [H2(OÄPMe2)*; (1)] is metalated with Fe(CO)5/I2 in toluene to yield an air-stable binuclear iron(III) porphodimethene, μ-oxobis(α, γ-dimethyl-α, γ-dihydrooctaethylporphinato)iron-(III) [(OÄPMe2)FeOFe(OÄPMe2); (2a)] after chromatography and crystallization. 2a is transformed into the mononuclear hemins Fe(OÄPMe2)X [X = OMe, OPh, OAc, Cl (2 b-2 e)] and into a nitrosyl heme Fe(OÄPMe2)NO (2f). Other hemes are identified in solution. The compounds are characterized by elemental analyses, electronic-, IR, and mass spectra. IR data and magnetic moments as measured in solution by the Evans method allow a distinction between the mononuclear and binuclear species. While the FeII porphodimethenes (hemes) show only one strong absorption in the visible region λ≈460 nm; like Zn(OÄPMe2), the FeIII species (hemins) have three characteristic strong bands (λ≈ 400, 450, and 540 nm for the μ-oxo species).

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