Metathetical reactions of [Rh₂Cl₂(μ-CPh₂)₂(μ-SbiPr₃)] 1 with NaBr and NaI afforded the corresponding di-nuclear complexes [Rh₂X₂(μ-CPh₂)₂(μ-SbiPr₃)] (X = Br 2, I 3) in practically quantitative yields. Analogous displacement reactions of 1 with equimolar amounts of the sodium salts of acetylacetone (acacH), trifluoracetylacetone (acac-f₃-H) and dipivaloylmethane (dpmH) led to the formation of the unsymmetrical rhodium(I) compounds [Rh₂(X)Cl(μ-CPh₂)₂(μ-SbiPr₃)] (X = acac 4, acac-f₃5, dpm 6). From 1 and excess of Na(acac) and Na(dpm), the symmetrical complexes [Rh₂X₂(μ-CPh₂)₂(μ-SbiPr₃)] (X = acac 7, dpm 8) were formed. Treatment of 7 with acetic acid and trifluoracetic acid in the molar ratio of 1 ∶ 1 gave the unsymmetrical compounds [Rh₂X(acac)(μ-CPh₂)₂(μ-SbiPr₃)] (X = CF₃CO₂9, CH₃CO₂10), while with an excess of CR₃CO₂H the symmetrical complexes [Rh₂(κ²-O₂CR₃)₂(μ-CPh₂)₂(μ-SbiPr₃)] (R = F 11, H 12) were obtained. The X-ray crystal structure analysis of 12 revealed that analogously to 1 the stibine ligand occupies a symmetrical bridging position. The reactions of 1, 4 and 7 with SbEt₃ and Sb(CH₂Ph)₃ led to bridge-ligand exchange and gave the di-nuclear compounds [Rh₂(acac)Cl(μ-CPh₂)₂(μ-SbEt₃)] 13 and [Rh₂X(X′)(μ-CPh₂)₂{μ-Sb(CH₂Ph)₃}] (X = X′ = Cl 14, X = Cl, X′ = acac 15, X = X′ = acac 16) without cleavage of the [Rh₂(μ-CPh₂)₂] core fragment.