[ReO(ppme)X] (where ppme(2-) is 2,5-diazo-N,N ' -dimethylhexyl-1,6-bis(phenylphosphinate), X = Br0.3Cl0.7) has been synthesized via a substitution reaction and structurally characterized. The coordination geometry is a distorted octahedron and one phosphinate coordinates cis and the other trans to the oxo O atom. This coordination mode is conserved in all [ReOppmeX] complexes synthesized in this study. [ReO(ppme)CI] has been prepared by a reduction/complexation reaction from [NH4][ReO4]. [ReO(ppme)Cl] reacts with thiocyanate and benzene thiolate forming [ReO(ppme)X] (X = -NCS, -SC6H5), but the one-pot synthesis of the respective. ternary thiolate complexes from perrhenate was not successful. The reduction/complexation reaction of a thiol, H(2)ppmeCl(4), and perrhenate resulted in the formation of [H(3)ppme][ReO(SR)(4)], the reaction of which with [ReO(ppme)CI] does not lead to [ReO(ppme)SR] in high yields.