The reactions of trans-[RhCl(CO)(DPM)] 2 (1) (DPM Ph 2PCH 2PPh 2) and [Rh 2Cl 2(μ-CO)(DPM) 2] (2) with CS 2 have been investigated and the final product of each reaction, [Rh 2Cl 2(CO)(C 2S 4)(DPM) 2] (3), has been structurally characterized by X-ray crystallography. A scheme for the reaction of 2 is presented based on monitoring the stepwise addition Of CS 2 using 31P 1H and 13C 31P{ 1H} NMR and infrared spectroscopy. The scheme for the reaction of 1 is based on infrared and 31P{ 1H} NMR data and on analogies with the reaction of 2, and with the similar, well characterized reactions of 1 with SO2. Compound 3 crystallizes in the space group P2 1/ c with a 22.311(3) Å, b 22.843(3) Å, c 22.828(3) Å, β 115.21(1)° and Z 8. Based on 5929 observed reflections the structure was refined to R 0.112 and R w 0.143 based on group refinement for the phenyl rings and isotropic refinement for all other non-hydrogen atoms. Slight differences in the geometries of the two independent dimers are observed resulting from different DPM phenyl ring orientations. However, the major features of the two dimers are the same, having a C 2S 4 fragment bridging two quasi-octahedral rhodium atoms and bound by a sulfur (RhS (dimers A&B) 2.347(7), 2.356(7) Å) and a carbon atom (RhC 1.90(2), 1.95(2) Å) to one rhodium center and by a sulfur atom (RhS 2.386(7), 2.393(7) Å) to the other rhodium center. Other relevant parameters are: Rh(1)Rh(2) 2.811(3), 2.810(3) Å; Rh(1)Cl(1) 2.428(6), 2.455(6) Å; Rh(2)Cl(2) 2.508(8), 2.527(8) Å; Rh(2)C(1)O(1) 1.87(2), 1.96(3) Å.