Fourpolymer-supportedFe-Cotetrametallicclustershavebeenpreparedbyionexchangeandligandexchange.TheirstructureswerecharacterizedbyIR,UV/visiblediffusereflectancespectraandelementalanalysis,andbyanalogywiththereferenceclusterPhCH2NMe3FeCo3(CO)2.Thefourheterogenousclusterswereefficientcatalystsinthehydroformylationof1-hexene,turnovernumbersamountedto823—924withtheyieldof83.2—92.4%heptylaldehydesandratiosofnormalaldehydetoiso-aldehydeof1.2—1.6,theyarefacilitatedformingthenormalaldehydeincomparisonwiththehomogeneousanalogue.Forthepolymer-supportedclusterspreparedbyionexchange,thepolymer-cationpartshadnoobviouseffectontheactivityoftheclusteranion.Thepolymer-phosphinesubstitutedclusterpreparedbyligandexchangewasmorestablethantheclusterspreparedbyionexchange.