Reactions of silver thiolates with bidentate phosphanes

Abstract A series of reactions of different silver thiolates, AgSR (R = Mes (mesityl), Nph (naphthyl), Cy (cyclohexyl)), with bidentate phosphanes was performed yielding a bunch of new compounds, which were characterized by single crystal X-ray diffraction. Depending on the nature of the thiolate and the phosphane the solid state structure of the products varies from discrete complexes or clusters to a 3-dimensional coordination network. The mesityl group favors the formation of trinuclear units which are then linked in one, e.g. [Ag 3 (SMes) 3 (dpph) 2 ] ( 5 ), two, e. g. [Ag 3 (SMes) 3 (dpppt) 2 ] ( 4 ), or three dimensions [Ag 3 (SMes) 3 (dppb) 2 ] ( 3 ), via the phosphanes. With naphthyl and cyclohexyl groups mostly clusters are formed which are either isolated with some phosphanes in their ligand sphere, e.g. [Ag 12 (SCy) 12 (dpppt) 2 ] ( 13 ), or additionally linked by the phosphanes to form 1-dimensional chains, e.g. [Ag 12 (SCy) 12 (dppo)] ( 17 ).