Core modified porphyrins – a macrocyclic platform for organometallic chemistry

An alteration of a metalloporphyrin coordination core, exemplified by 21-heteroporphyrins and 2-aza-21-carbaporphyrin (N-confused porphyrin, inverted porphyrin), provides a route of choice to stabilize unusual oxidation states and coordination geometries, affording a stabilization of such rare species as organometallic high-spin nickel(II) or copper(II) derivatives. This review focuses on reactivity and electronic structure of peculiar organometallic compounds trapped due to the appropriate choice of the suitable macrocyclic platform.