The employment of 2-pyrrolyloximes in high-nuclearity transition-metal cluster chemistry has provided access to unprecedented decanuclear and dodecanuclear Fe-III cagelike clusters bearing the anion of pyrrole-2-carboxaldehyde oxime (praoH(2)), the simplest member of this new family of ligands; the identity of the products depends on the nature of the counteranion present in the starting materials.