CpIr(η 4-C 6H 6) ( 2) has been obtained in high yield by a four-step synthesis. Thermal reaction of 2 with CpCO(C 2H 4) 2 and photochemical reaction of 2 with CpRh(C 2H 4) 2 or Cp★Rh(C 2H 4) 2 give the compounds μ-(η 3: η 3-C 6H 6)CoIrCp 2 ( 3), μ-(η 3: η 3-C 6H 6)RhIrCp 2 ( 4), and μ-(η 3: η 3-C 6H 6)(RhCp★)(IrCp) ( 5), respectively. The X-ray crystallography data of 3 and 4 reveal a boat-shaped conformation of the synfacially bridging benzene ligand with a rather long CoIr bond distance in 3 and a relatively short RhIr bond length in 4 which are caused by almost constant folding angles of the benzene unit. The dynamic behaviour of the benzene bridge was investigated by NMR spectrometry.