The extent of metal–metal electronic coupling was quantified for a series of syn and anti stereoisomers of (FeCp)2-, (RhL2)2- and (FeCp)(RhL2)- (L2=1,5-cyclooctadiene (cod), L=CO) as-indacenediide mixed-valent ions by spectroelectrochemical and DFT studies. The effect of the syn/anti orientation of the metal units with respect to the planar aromatic ligand indicates that electron transfer occurs through the bridge rather than through space. The nature of the metal was found to be crucial: while homobimetallic diiron species are localised valence-trapped ions (Class II), the dirhodium analogues are almost delocalised mixed-valent ions (borderline and Class III). Finally, despite their redox asymmetry, even in the heterobimetallic iron–rhodium as-indacenediide complexes, strong metal–metal coupling is present. In fact, oxidation of the iron centre is accompanied by electron transfer from rhodium to iron and formation of a reactive 17-electron rhodium site. syn and anti Fe–Rh as-indacenediide complexes are rare examples of heterobimetallic systems which can be classified as borderline Class II/Class III species.