A Dodecanuclear Copper(I) Complex Containing a Cubic (CuS)4 Core Stabilized by a Tripodal (N,N,P)-Chelating Ligand

Recently, we reported on main group metal complexes of tridentate polyimido sulfur ligands with a phosphorus [1] or a nitrogen [2, 3] side-arm. These monoanionic ligands have the general formulae {R2PCH2S(NR)2} (R1 = Me, Ph; R2 = tBu, SiMe3) and {R2N(spacer)S(NR)2} (R1 = Me; R2 = tBu, SiMe3, spacer = 0, (CH2)n, C6H4). Metal complexes are accessible via salt elimination from the dimer [Li{Me2PCH2S(NR)2}]2 and MgCl2. However, this route was so far only successful with MgCl2, which is probably due to the diagonal relationship between lithium and magnesium. We now wanted to widen the route to other metal complexes by other reagents than metal halides. This is of great interest, because it is known that such halides can initiate S–N bond cleavage reactions in sulfur diimido compounds [4]. To prevent this ligand scrambling, the copper(I) amide [Cu{N(SiMe3)2}] was employed in a transmetallation reaction.