A dithiocarbamate-stabilized copper(I) cube

The disproportionation reaction between the copper(II) complexes, Cu(ClO4)2 · 6H2O and [Cu(S2CNR2)2] is a well-established route to copper(III) complexes [Cu(S2CNR2)2][ClO4] but to date the nature of the copper(I) species generated has remained a mystery. We now show that with [Cu(S2CNPr2)2] this is the copper(I) cluster, [Cu8(μ2,μ2-S2CNPr2)6][ClO4]2, which contains a cubic array of copper atoms, each face cube being capped by a dithiocarbamate ligand such that the sulfur atoms define an icosahedron and the backbone carbons an octahedron around the cube centroid. A crystal structure of [Cu4(μ2,η1-S2CNBu2)4] is also presented for comparison.