The metalloporphyrins containing fragments of 1,3-nitroketones on periphery of macrocycle was obtained by nitration of copper complexes of isomeric ketoporphyrins by mixture of nitrogen oxide NO2 and dinitrogene tetroxide N2O4. Catalytic reduction of nitro groups in these compounds by palladium on carbon leads to corresponding 1,3-enaminocetones, which capable to exo-coordination with ions of transition metals.