New copper selenium clusters with a sulfur functionalised ligand shell

We introduce two new sulfur functionalised phosphines P(C6H4SMe)3L1 and PPh2C6H4SMe L2. Using them as ligands, four new copper selenium clusters were synthesized. The compounds [Cu15Se3(SePh)9(P(C6H4SMe)3)6] 1, [Cu22Se6(SePh)10(PPh2C6H4SMe)8] 2, [Cu20Se(SePh)12(OAc)6(PPh2C6H4SMe)2] 3 and [Cu38Se4(SePh)24(OAc)6(PPh2C6H4SMe)4] 4 were characterized by single crystal X-ray analysis and demonstrate the coordination of the phosphines through the phosphorus atoms. The thiomethyl groups of the ligands are not coordinated to any metal centre, but are located on the surface of the organic shell of the cluster molecules. This may provide an opportunity for further reactions between the functionalised clusters and metal atoms or surfaces. Furthermore the inner cluster cores show arrangements of copper and selenium atoms not yet found in these kinds of compounds.