Structural characterization of silver(I) complexes [Ag(O3SCF3)(L)] (L=PPh3, PPh2Me, SC4H8) and [AgLn](CF3SO3) (n=2–4), (L=PPh3, PPh2Me)

We have studied the solution and some solid state structures of a series of trifluoromethanesulfonate silver(I) complexes, namely of formula [Ag(O3SCF3)(L)] (L=PPh3, PPh2Me, SC4H8) and [AgLn](CF3SO3) (n=2–4, L=PPh3, PPh2Me). The solution behaviour is as expected for mononuclear silver species, although polynuclear species can not be totally ruled out in non-coordinating solvents. The solid state structures display a wide variety of nuclearities, silver co-ordination numbers and trifluoromethanesulfonate co-ordination modes, depending on the ligand L. Thus, for complexes of empirical formula [Ag(O3SCF3)(L)], the crystal structure of [Ag(O3SCF3)(PPh3)] is a trimer with bridging triflates; the molecular structure of [Ag(O3SCF3)(PPh2Me)] shows tetranuclear complexes with a ‘chair’ geometry, further linked into chains by Ag–phenyl interactions; and [Ag(O3SCF3)(tht)] (tht=SC4H8) crystallizes in infinite chains. For complexes of formula [Ag(O3SCF3)(L)2], the PPh3 derivative is a dimer with two bridging triflates, and the PPh2Me derivative is a monomer.