Abstract
Three five-coordinate iron acetate porphyrin complexes, (por)Fe(OC(=O)R) (por=porphyrinato dianion; R=CCl3, CH2Cl), have been synthesized and characterized. The crystal structure of (TPP)Fe(OC(=O)CCl3) (TPP=tetraphenylporphyrinato dianion) has been determined by X-ray crystallography. The redox behaviors of the (por)Fe(OC(=O)R) compounds have been investigated by cyclic voltammetry and infrared spectroelectrochemistry. Analysis of the data reveals that the first oxidations of the (por)Fe(OC(=O)R) compounds are porphyrin-centered processes to yield π-radical cations of the form (por+)Fe(OC(=O)R), and the first reductions may facilitate the dissociation of the axial acetate ligands from the iron centers.
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