Meso-substituted corroles bearing peripheral donor sites

Various pathways towards corroles bearing additional donor sites especially those with diazacrown units have been evaluated. Macrocyclic diamidation based on the reaction of diamines with diesters was found to be the key step in the overall synthetic scheme. This strategy was applied successfully to the synthesis of three compounds possessing macrocyclic diamide or diamine moieties. In addition, a meso-picolyl derivatized corrole was prepared. The new ligands were investigated with respect to the regioselectivity of transition metal insertion. Mononuclear corrolates of copper and cobalt are formed as the only isolable products, if simple copper and cobalt precursors and standard metalation protocols are applied. The results prove, that corroles can be used as selectively coordinating building blocks in multi-compartment ligand systems with peripheral crown ether and pyridyl functionalization. Copyright (c) 2006 Society of Porphyrins & Phthalocyanines.