A series of complexes of the general formula [(η6-arene)RuCp][PF6] (where arene = aryl halides or nitroarenes) were synthesised and the arene ring was found to be reactive towards an intermolecular nucleophilic aromatic substitution (SNAr) reaction with a series of cyclic 1,3-diones. Competition experiments indicated that leaving group ability of the aryl halides and nitroarenes went in the order of F ≫ NO2 > Cl > Br. Following SNAr, the arene rings were liberated quantitatively via a rapid photolysis reaction (<15 min).