Reactions of [MoO(S(2)CNR(2))(3)]BF4 with boron sulfide in dichloromethane result in the formation of [Mo-2(mu-S-2)2(S(2)CNR(2))4](BF4)2 [R = Et (1), Pr-i (2), Bu(i) (3)] and [Mo(S(2)CNR(2))(4)]BF4. Reactions of WS(S-2)(S(2)CNR(2))(2) with Me(3)SiI in dichloromethane produce [W-2(mu-S-2)(2)(S(2)CNR(2))(4)]I(I-3) (R = Et (4), Bu(i) (5)). The air stable, diamagnetic compounds have been characterized by microanalytical, mass spectral, IR,H-1 NMR and crystallographic studies. Orange 1.2CHBr(3) crystallizes in triclinic space group P (1) over bar with a = 12.560 (3), b = 13.000 (4), c = 8.071 (4) Angstrom, alpha = 94.16 (4), beta = 90.09 (3), gamma = 75.80 (2)degrees, V = 1274 (1) Angstrom(3) and Z = 1 dimer. Orange-red 4 crystallizes in triclinic space group P (1) over bar with a = 13.798 (3), b = 11.876 (3), c 15.182 (4) Angstrom, alpha 106.95 (2), beta = 112.26 (2), gamma 84.70 (2)degrees, V = 2202 (1) Angstrom(3) and Z = 2. The structures were solved by Patterson and Fourier methods followed by least-squares refinements to conventional R values of 0.036 and 0.069 for 1 and 4, respectively. The Mo- and W-containing cations exhibit dinuclear structures wherein M(V) centers are bridged by two mu-kappa(2)S,S:kappa(2)S,S’-S-2(2-) (mu-S-2(2-)) ligands [S-S average 2.01 Angstrom] and a metal-metal single bond [Mo-Mo 2.808 (1) Angstrom; W-W = 2.792 (3) Angstrom]]. Each metal atom is further coordinated by two bidentate dithiocarbamate ligands, the arrangement of which defines a Delta Lambda diastereomer.