5,6-Dimethoxyphenanthriporphyrin 1 and 5,6-dioxophenanthriporphyrin 2 act as suitable organometallic ligands for copper(III), adopting trianionic [CCNN] coordination cores. Under oxidizing conditions, in the presence of methanol, copper(III) phenanthriporphyrin 1-Cu undergoes transformation to copper(III) phenanthriporphodimethene with methoxy substituents attached to two trans meso positions. Addition of acids to 1-Cu yields two isomeric copper(III) isophenanthriporphyrins protonated on one of the meso carbon atoms. Protonation of copper(III) 5,6-dioxophenanthriporphyrin 2-Cu yields the aromatic diprotonated complex 2-Cu-H22+. In the presence of HBF4 2-Cu undergoes borylation at the carbonyl oxygen atoms, forming an aromatic exocyclic boron(III) complex.