The synthesis and characterization of a series of arene ruthenium complexes bearing either (3,5-cycloheptadienyl)diphenylphosphine or (cycloheptyl)diphenylphosphine are reported. Upon irradiation or heating, all these complexes lose their arene ligand but then exhibit a different behavior depending on the nature of the phosphine ligand. (Cycloheptadienyl)phosphine complexes 1 and 3 give a cationic dinuclear Ru complex 5 for which the two Ru atoms are bridged by three chlorido ligands and flanked by two tridendate (cycloheptadienyl)phosphines. (Cycloheptyl)diphenylphosphine complexes 2 and 4 undergo arene exchange when toluene is used as solvent or degrade in dichloromethane. ATRA catalytic trials conducted in parallel with these complexes using CCl4 and styrene as standard substrates, highlighted the deep impact of the dienyl moiety on the results. Under smooth conditions (UV irradiation or moderate heating), only (cycloheptyl)phosphine derivatives give Karasch adduct in satisfactory yields. Their perform...