Structural diversity in copper-sulfur chemistry: synthesis of novel Cu/S clusters through metathesis reactions.

With the ultimate goal of understanding the Cu(4)S cluster in nitrous oxide reductase, studies of the fundamental chemistry of nitrogen-donor ligand-supported copper-sulfur species have been pursued. Reactions of Cu(II)X(2) (X = Cl(-) or CF(3)SO(3)(-)), N,N,N',N'-tetramethyl-trans-(1R,2R)-diaminocyclohexane, and Li(2)S or Na(2)S(2) yielded clusters that contain [Cu(2)(micro-S(2))(2)](2+), [Cu(3)(micro-S)(2)](3+), [Cu(4)(micro-S(2))(2)](4+), and/or [Cu(6)(micro-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 S(2-), S(2)(2-), and S(2)(-*), were identified by X-ray crystallography and spectroscopy.