Coordination of d10-metal cations by thiacycloalkynes

Article abstract of DOI:10.1016/S0277-5387(96)00435-4

A range of complexes has been prepared by reaction of thiacycloalkynes with Ag¹, Cu¹ and Hg¹¹ cations and cationic MPR₃ (M = Ag, Cu, Hg) fragments. ¹H NMR studies reveal that coordination of 1,4,7-trithiacycloundec-9-yne (L¹) to Ag¹ results in a change of ligand conformation from exodentate in the free ligand to endodentate in the coordinated ligand implying involvement of the thioether functionalities in coordination. Participation of the alkyne linkage in coordination is less certain and a polymeric structure is suggested in the solid state. Reaction of AgSbF₆ with L¹ and PPh₃ or PMe₂Ph afforded complexes in which the silver is coordinated by a phosphine and an endodentate η³-L¹. Similar studies with Cu^I and Hg^II showed a reduced tendency for thioether coordination reflected in a reduced denticity of L¹. Studies with a range of dithiacycloalkynes and a tetrathiacyclodiyne show that Ag⁺ and Cu⁺ can be successfully coordinated by ligands containing a combination of two thioether donors and one alkyne.