Abstract
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.
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