The first series of Rh(I) distibine complexes with organometallic co-ligands is described, including the five-coordinate [Rh(cod)(distibine)Cl], the 16-electron planar cations [Rh(cod)(distibine)]BF₄ and [Rh{Ph₂Sb(CH₂)₃SbPh₂}₂]BF₄ and the five-coordinate [Rh(CO)(distibine)₂][Rh(CO)₂Cl₂] (distibine = R₂Sb(CH₂)₃SbR₂, R = Ph or Me, and o-C₆H₄(CH₂SbMe₂)₂). The corresponding Ir(I) species [Ir(cod)(distibine)]BF₄ and [Ir{Ph₂Sb(CH₂)₃SbPh₂}₂]BF₄ have also been prepared. The complexes have been characterised by ¹H and ¹³C{¹H} NMR and IR spectroscopy, electrospray mass spectrometry and microanalysis. The crystal structure of the anion exchanged [Rh(CO){Ph₂Sb(CH₂)₃SbPh₂}₂]PF₆·3/4CH₂Cl₂ is also described. The methyl-substituted distibine complexes are less stable than the complexes of Ph₂Sb(CH₂)₃SbPh₂, with C–Sb fission occurring in some of the complexes of the former. The salts [Rh(CO){Ph₂Sb(CH₂)₃SbPh₂}₂]PF₆ and [Rh{Ph₂Sb(CH₂)₃SbPh₂}₂]BF₄ undergo oxidative addition with Br₂ to give the known [RhBr₂{Ph₂Sb(CH₂)₃SbPh₂}₂]⁺, while using HCl gives the same hydride complex from both precursors, which is tentatively assigned as [RhHCl₂{Ph₂Sb(CH₂)₃SbPh₂}]. An unexpected further Rh(III) product from this reaction, trans-[RhCl₂{Ph₂Sb(CH₂)₃SbPh₂}{PhClSb(CH₂)₃SbClPh}]Cl, was identified by a crystal structure analysis and represents the first structurally characterised example of a chlorostibine coordinated to a metal. [Rh{Ph₂Sb(CH₂)₃SbPh₂}₂]BF₄ reacts with CO to give [Rh(CO){Ph₂Sb(CH₂)₃SbPh₂}₂]BF₄ initially, and upon further exposure this species undergoes further reversible carbonylation to give a cis-dicarbonyl species thought to be [Rh(CO)₂{Ph₂Sb(CH₂)₃SbPh₂}{κ¹Sb-Ph₂Sb(CH₂)₃SbPh₂}]BF₄ which converts back to the monocarbonyl complex when the CO atmosphere is replaced with N₂.