The properties of the carbon sulfide C6S8 (1) as well as its dioxo analogue C6S6O2 (2) have been studied in the fully oxidized and fully reduced forms, i.e., 10, 1,2- 20, 22-. A crystallographic study shows that compound 2 is a tricyclic species with a twisted 1,2-dithiin (unsaturated C4S2 ring) core. Reduction of 1 with 2 equiv of LiBHEt3 gave C6S82- (12-), which was isolated as its PPh4+ salt. A crystallographic study of this salt shows that reduction has resulted in cleavage of the S−S bond and that, in the solid state, the dihedral angle between the two rings is 180°. Both 12- and 22- undergo two sequential and reversible 1e- oxidations near 0 V (vs Ag/AgCl), thus establishing that 10 and 20 are good oxidants relative to other disulfides. Treatment of (PPh4)2[C6S8] with [Ni(H2O)6]Cl2 afforded the dark red (PPh4)2[Ni(C6S8)2] (3). The analogous Pt complex (4) was also prepared. Crystallographic analysis of 3 shows that the nickel center is square planar, comprising two seven-membered NiS2C4 rings. The paramagnetism observed for solutions of 3 are attributed to the formation of a tetrahedral isomer.