The interaction of dicarbonylchlororhodium(I) dimer with cyclopropane produces a dimeric complex, [(C3H6CO)RhCl(CO)]2, which involves rhodium(III) in a five-membered ketonic heterocycle together with bridging halogens. The bridge can be cleaved by aromatic amines or triphenylphosphine (L) to give either a monomeric complex, (C3HC6O)RhCIL2, or the salt [(C3H6CO)Rh(CO)L2]Cl, where the heterocyclic ring is retained.Perfluorobutadiene and [RhCl(CO)2]2 give again a rhodium(III) complex, [(C4F6)Rh(CO)2Cl]2, with the metal atom in an unsaturated perfluoroheterocycle.Perfluorobutadiene and tris(triphenylphosphine)chlororhodium(I) also give a complex with a diolefinic heterocycle formed through loss of two fluorine atoms and of constitution (C4F4)RhCl(PPh3)2. By contrast buta-1,3-diene gives a chelating diolefin complex of rhodium(I), (C4H6)RhCl(PPh3)2.The complexes are characterised inter alia by i.r. and n.m.r. spectroscopy.
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Roundhill et al. (1968) studied this question.