Chemistry of iron 10-heterocorroles

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10-Heterocorroles are a class of porphyrinoid macrocycles that have been made synthetically accessible recently in our group. The most intriguing feature of these porphyrin analogs lies in the geometry of the N4-binding site, whose size can be fine-tuned through the use of different heteroatoms at the 10-position. The different size of the binding site directly influences the electronic structure of metal complexes of these ligands. First results on iron complexes show that the altered electronic features lead not only to distinctive spectroscopic pattern, but also seems to be reflected in new reactivity profiles.In this project, iron complexes of 10-heterocorrole model ligands with oxygen, sulfur, selenium and nitrogen heteroatoms in the 10 position will be prepared and characterized in detail with respect to their unique electronic structures (Mössbauer, and EPR spectroscopy, SQUID magnetometry). The reactivities of these complexes will then be studied systematically as a function of the size of the N4 binding site. Of particular interest are a potential utility as a bioinorganic model for cytochrome c', and a possible suitability for the stabilization of iron in high oxidation states.