The synthesis and characterization of molecular carbon sulfides including C3S8, C6S8, C6S10, and C6S12 are described. The reaction of 2 equivs of S2Cl2 with (NBu(4))2[Zn(C3S5)(2)] (1) affords a 2:1 mixture of C3S8 and C6S12 Treatment of this mixture with excess Hg(OAc)2 gives the soluble yellow species C3S7O. This compound crystallizes in the triclinic space group P (1) over bar with a = 4.204(2) Angstrom, b = 8.942(5) Angstrom, c = 12.017(6) Angstrom, alpha = 103.02(4)degrees, beta = 96.64(4)degrees, gamma = 90.47(4)degrees, and Z = 2. The oxidation of 1 with 2 equiv of SO2Cl2 and subsequent extraction of the orange solid with CS2 yielded the dimer C6S10 Raman spectra indicate that the crude oxidation product is modified upon extraction, possibly by break-up of the polymer (C3S5)(n). Treatment of C6S10 With 2 equivs of Hg(OAc)(2) results in rearrangement of the central C4S4 ring in addition to a C=S to C=O exchange, to give a 1,4,5,6-tetrathiacycloheptadiene ring. C6S8O2 crystallizes in the monoclinic space group P2(1)/c, with a 15.461 (6) Angstrom, b = 9.648(3) Angstrom, c = 7.852(1) Angstrom, beta = 98.71(2)degrees, and Z = 4. The C-13 NMR spectrum of C6S8O2 exhibits resonances at delta 187.0, 137.5, and 130.8 in agreement with the crystal structure. Treatment of 1 with 4 equivs of HCl at -78 degrees C gave the metastable C3S5H2 as characterized by H-1 NMR, FDMS, and IR spectroscopies, as well as its conversion to C(3)S(5)Me(2). This dithiol evolves H2S, giving a new compound of the formula C6S8. This species was converted with Hg(OAc)(2) to C6S6O2, which is formulated as a derivative of a c-1,2-S2C4 compound based on spectroscopic and elemental analysis data. Treatment of (Bu(4)N)2[Zn(C3S5)(2)] with 4 equiv of SO2Cl2 gave the sulfenyl chloride C3S5Cl2, which in turn reacts with LiN(SiMe(3))2 and Me(3)Si(3) to give C3S5[N(SiMe(3))(2)](2) and C3S5NCl, respectively.