With the ultimate goal of understanding the CU4S cluster in nitrous oxide reductase, studies of the fundamental chemistry of nitrogen-donor ligand-supported copper-sulfur species have been pursued. Reactions Of (CUX2)-X-II (X = Cl- or CF3SO3-) N,N,N ',N '-tetramethyl-trans-(1 R,2R)-diaminocyclohexane, and Li2S or Na2S2 yielded clusters that contain [Cu-2(mu-S-2)(2)](2+), [Cu-3(mu-S)(2)](3+), [Cu-4(mu-S-2)(2)](4+), and/or [Cu-6(mu-S-2)(4)](4+) cores, depending on the specific reaction conditions, notably the nature of X and the sulfur source used. Copper(II) and/or Copper(III) and variable sulfur oxidation levels, including S2-, S-2(2-), and S-2(-center dot), were identified by X-ray crystallography and spectroscopy.