Di- and monoaminated polystyrenes of I and II were prepared by reactions of chloromethylated polystyrene with N,N-dimethyl-1,3-propanediamine and diethylamine, respectively. Treatment of the diaminated polystyrene (I) with Fe-3(CO)(12) in aqueous medium at 50 degrees C for 6 h gave a polymer-bound [Fe-3(CO)(11)](2-) complex. However, under refluxing conditions, a polymeric [Fe-4(CO)(13)](2-) complex was formed. When Fe(CO)(5) was used as a starting material, selective formation of the above Fe-4 complex resulted after a long reaction time, 16 h. Treatment with Fe(CO)(5) at room temperature afforded a polymeric [HFe(CO)(4)](-) complex. Reactions of II with Fe-3(CO)(12) and Fe(CO)(5) attained selective generation of a [HFe3(CO)(11)](-) species in the polymer, respectively. Furthermore, these polymer-bound Fe-3 and Fe-4 complexes could be also obtained by ion exchange reactions of both I and II with the corresponding ionic Fe compounds. Reaction of I with Ru-3(CO)12 at room temperature for 24 h gave polymer-bound [HRu3(CO)(11)](-) complex. [Ru-6(CO)(18)](2-) species could be selectively fixed in I by using the above ion exchange method. The Fe and Ru carbonyl anionic species are stabilized through forming an ion pair in the polymer matrix.