New rhenium sulfide complexes, [Re-2(IV)(mu-S)(2)(mu-S-2)(mu-S2COR)(S2COR)(2)](-) and [Re-2(IV)(mu-S)(2)(S2COR)(4)], and a new tungsten sulfide complex, [WS(S-2)(S2CC6H5)(2)], have been synthesized and isolated via induced internal redox reactions involving the appropriate tetrathiometalate and 1,1-dithiolate disulfide. The red complex [Re-2(IV)(mu-S)(2)(mu-S-2)(mu-S2COR)(S2COR)(2)](-), 1, was isolated from the reaction of dialkylxanthogen disulfide, [(ROCS2)(2)], and tetraethylammonium tetrathioperrhenate, [Et4N][(ReS4)-S-VII]. Crystal structure analysis of 1 reveals an edge-sharing (mu-S)(2) bioctahedron containing both bridging disulfide and xanthate ligands. This reaction is compared to the known reaction between tetraalkylthiuram disulfide, [(R2NCS2)(2)], and [Et4N][ReS4], which produces the green complex [Re-2(IV)(mu-S)(2)(S2CNR2)(4)]. The corresponding green alkyl xanthate analogue, [Re-2(IV)(mu-S)(2)(S2COR)(4)], 2, was synthesized by a simple redox reaction between rhenium pentachloride, ReCl5, and potassium alkyl xanthate, [K(S2COR)]. Comparing 1 with other known [ReS4](-)/1,1-dithiolate disulfide reaction products, such as [ReN2(mu-S)(2)(S2CNR2)(4)] and [Re-III(S2CC6H5)(S3CC6H5)(2)], shows a correlation between the electron-donating ability of the ligand and the nature of the reaction product. Reactions of [Et4N](2)[(MoS4)-S-VI], [Et4N][(ReS4)-S-VII], Or [Et4N](2)[(WS4)-S-VI] with dithiobenzoate disulfide, [(S2CC6H5)(2)], reveal a correlation between the ligand-to-metal charge transfer energy band (LMCT1) of the tetrathiometalate and the reaction product. The known purple complex [Mo-IV(S2CC6H5)(4)] and two new green complexes, [Re-III(S2CC6H5)(S3CC6H5)(2)] (recently communicated) and [(WS)-S-VI(S-2)(S2CC6H5)(2)], were isolated from related reactions.