Synthesis and characterization of six-coordinate iron(II/III) 5,10,15,20-tetrakis(pentafluorophenyl) porphyrinato complexes with non-hindered imidazole ligands
Four bis-imidazole iron(II/III) 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato (TFPP) complexes, [Fe(TFPP)(1-MeIm)[Formula: see text]], [Fe(TFPP)(1-VinylIm)[Formula: see text]], [Fe(TFPP)(4-MeHIm)[Formula: see text]]Cl and [Fe(TFPP)(1-EtIm)[Formula: see text]]BF[Formula: see text] (1-MeIm [Formula: see text] 1-methylimidazole, 1-VinylIm [Formula: see text] 1-vinylimidazole, 4-MeHIm [Formula: see text] 4-methylimidazole and 1-EtIm [Formula: see text] 1-ethylimidazole) were synthesized and characterized by single-crystal X-ray and UV-vis spectroscopy. A negative correlation is found between the absolute imidazole orientation ([Formula: see text] and the Fe–N[Formula: see text] distance for the [Fe(II)(Porph)(Im)[Formula: see text]] (Im [Formula: see text] 1-MeIm or 4-MeHIm) complexes where the smaller [Formula: see text] angle corresponds to a longer axial distance. Hydrogen bonding, which might affect the orientations of the axial imidazoles is found for Fe(TFPP)(4-MeHIm)[Formula: see text]]Cl (A and B). The autoreduction of [Fe(III)(TFPP)]Cl to [Fe(II)(TFPP)(1-MeIm)[Formula: see text]] with 1-methylimidazole has been monitored by UV-vis spectroscopic titration.