A convenient procedure for the synthesis of fluoro-iron(III) complexes of common synthetic porphyrinates

Abstract

We report here an improved method for the preparation of fluoro-iron(III) porphyrinate complexes. Treatment of [ Fe 2( P )2(μ- O )] (P = tetraphenylporphyrinate {TPP}, tetra-p-tolylporphyrinate {TTP}, or octaethylporphyrinate {OEP}) or [ Fe ( OH )( OH 2)( TMP )] (TMP = tetramesitylporphyrinate) with the commercially available fluorinating agent, Et 3 N ·3 HF , in dichloromethane affords the desired [ FeF ( P )] complexes in a straightforward fashion and in good yield while avoiding the use of aqueous hydrofluoric acid. All fluoro-iron(III) complexes have been completely characterized by a series of different spectroscopic techniques including cyclic voltammetry. Reaction of a representative complex, [ FeF ( OEP )], with various chloride reagents demonstrates that halide exchange with chloride is facile, but only proceeds at an appreciable rate in the presence of proton sources. Unexpectedly, treatment of [ FeF ( OEP )] with NOBF 4 did not to lead formation of an oxidized species, but rather to formation of the { Fe – NO }6 complex, [ Fe ( NO )( OEP )]( BF 4).