Reactions directed at the synthesis of structural analogues of the active site of molybdenum-containing carbon monoxide dehydrogenase have been investigated utilizing [WO2S(bdt)](2-) (1) and [WOS2(bdt)](2-) (2) and sterically hindered [Cu(R)L] or [Cu(SSiR '(3))(2)](-) as reactants. All successful reactions of 2 afford the binuclear W-VI/Cu-I products [WO(bdt)(mu(2)-S)(2)Cu(L)](2-/-) with L = carbene (3), Ar*S (4), Ar* (7), SSiR3 (R = Ph (5), Pr-i (6)). Similarly, [W(bdt)(OSiPh3)S-2](-) leads to [W(bdt)(OSiPh3)(mu(2)-S)(2)Cu(SAr*)](-) (8). These complexes, with apical oxo and basal dithiolato and sulfido coordination (excluding 8), terminal thidate ligation at Cu-I (4-6, 8), and W-(mu(2)-S)-Cu bridging, bear a structural resemblance to the enzyme site, Differences include two bridges instead of one and the absence of basal oxo/hydroxo ligation. Complex 8 differs from the others by utilizing apical and basal sulfido ligands in bridge formation. Related reaction systems based on 1 gave 4 in small yield or product mixtures in which the desired monobridged complex [WO2(bdt)(mu(2)-S)Cu(R)](2-) was not detected. Mass spectrometric analysis of the reaction system with L = carbene suggests that any monobridged species forms may converted to the dibridged form by disproportionation. In these experiments, the use of W-VI preserves the structural integrity of Mo-VI, whose analogues of 1 and 2 have not been isolated. (Ar* = 2,6-bis(2,4,6-triisopropylphenyl)phenyl, bdt = benzene-1 2-dithiolate(2-)).