Reactions of silver thiolates with bidentate phosphanes

•Reactions of silver thiolates with bidentate phosphanes yield a bunch of new compounds.•The silver thiolate units form clusters of different nuclearity up to 15 silver atoms.•The clusters act as knots in the formation of polymeric structures.•1-, 2- and 3-dimensional cross-linking can be achieved.

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. [Ag3(SMes)3(dpph)2] (5), two, e. g. [Ag3(SMes)3 (dpppt)2] (4), or three dimensions [Ag3(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. [Ag12(SCy)12(dpppt)2] (13), or additionally linked by the phosphanes to form 1-dimensional chains, e.g. [Ag12(SCy)12(dppo)] (17).

Graphical abstractReactions of silver thiolates with bidentate phosphanes give rise to a bundle of new compounds with different dimensionality. Depending on the thiolate and the phosphane isolated clusters or coordination polymers are yielded.In the polymers polynuclear (AgSR)n knots are cross-linked via the phosphanes in either one, two or three dimensions.Figure optionsDownload full-size imageDownload as PowerPoint slide