Iron and copper complexes of tetraphenyl-m-benziporphyrin (TP-mBPH)H have been prepared and structurally characterized. The iron system, (TPmBPH)(FeBr)-Br-II, contains a high-spin Fe(II) center. In the solid state the complex forms dimeric units linked by weak Cr...Br hydrogen bonds. The Cu complex contains a tetrameric copper cluster with a Cu2Cl42- unit bridging two [(TPmBPCl)Cu-II](+) fragments. The formation of (TPmBPCl)H represents an example of copper-catalyzed chlorination on the internal carbon atom of (TPmBPH)H.