Synthesis of (phosphine)silver(I) trifluoromethanesulfonate complexes and the molecular structure of di-μ-trifluoromethylsulfonate-(tetrakis-triphenylphosphine)disilver(I)

Abstract Reactions of silver trifluoromethanesulfonate (triflate) and equimolar amounts of triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, bis(diphenylphosphino)methane, or 1,1-bis(diphenylphosphino)ethane in either DME or CH 2 Cl 2 solution produced the corresponding 1:1 complexes [(L)Ag(I)(SO 3 CF 3 )] ( 2 – 5 ) in >80% yields. A related 2:1 complex [(Ph 3 P) 2 Ag(I)(SO 3 CF 3 )] ( 1 ) was also obtained using 2 equiv. of Ph 3 Ph. Both 31 P NMR variable temperature solution spectra as well as solid state spectra were recorded for the new complexes, and were generally helpful in structural assignments. An X-ray crystallographic study of 1 shows this to be a dimeric complex with bridging triflate ions; the silver atoms having distorted tetrahedral coordination.