The hitherto unknown series of complexes fac-[Re(CO) 3 Br{R 2 P(S)P(S)R 2 }] 1a-5a (1a, R=Me; 2a, R=Et; 3a, R= n Pr; 4a, R= n Bu; 5a, R=Ph) and [Re 2 (CO) 8 Br 2 {cis-μ-R 2 P(S)P(S)R 2 }] 1b-5b [1b, R=Me; 2b, R=Et; 3b, R= n Pr; 4b, R= n Bu; 5b, R=Ph] have been prepared by the photochemical reaction of Re(CO) 5 Br with R 2 P(S)P(S)R 2 . The complexes have been characterized by elemental analysis, mass spectroscopy (EI), FT-IR and 3 1 P{ 1 H} NMR spectrometry. The spectroscopic studies suggest cis-chelate bidentate coordination of the ligand in fac-[Re(CO) 3 Br{R 2 P(S)P(S)R 2 }] and cis-bridging bidentate coordination of the ligand between two metals in [Re 2 (CO) 8 Br 2 {cis-μ-R 2 P(S)P(S)R 2 }] (R=Me, Et, n Pr, n Bu, Ph). An X-ray diffraction study of [ReBr(CO) 3 (Et 2 P(S)P(S)Et 2 )] confirms that the rhenium adopts a distorted octahedral geometry with local C s symmetry.