Picket fence porphyrin challenges. Unexpected atropisomerism

Abstract

The synthesis and structural analysis of two new bis imidazole-ligated iron(II) porphyrinates are reported. The reacting porphyrin used in the studies was the four-coordinate [Formula: see text] atropisomer of [Fe(TpivPP)] (picket fence porphyrin); the axial ligands are 2-methylimidazole and 1,2-dimethylimidazole. Crystal structure analysis revealed that the [Fe(TpivPP)(2-MeHIm)[Formula: see text]] complex had a strongly ruffled porphyrin core that accommodated the hindered ligands on both the picket side and the open face of the porphyrin. Reaction with 1,2-dimethylimidazole with the four-coordinate [Fe(TpivPP)] starting material led to an isomerized form of the picket fence porphyrin. The structure analysis showed that the product obtained was the [Formula: see text] atropisomer. Strong ruffling caused by the bulky 1,2-dimethylimidazole ligand must allow the requisite rotation about the methine carbon to phenyl carbon single bond and yields what is probably the most stable form of the complex. The relative orientation of the two axial ligands in both complexes are approximately perpendicular to each other. Other structural parameters are in general accord with six-coordinate iron(II) porphyrinates.