Mono and Poly-nuclear Silver(I) Complexes with Thiosaccharin and Triphenylphosphine. Synthesis, Spectroscopic and Structural Characterization of Thiosaccharinato-bis(triphenylphosphine)silver(I) and Tetrakis{thiosaccharinato(triphenylphosphine)silver(I)}

Abstract

The reaction of Ag6(tsac)6 (1) (tsac = thiosaccharinate anion) with triphenylphosphine gives rise to the already reported [Ag(tsac)(PPh3)3] complex (2) and to two new silver-thiosaccharinate-phosphine complexes, [Ag(tsac)(PPh3)2] (3) and [Ag4(tsac)4(PPh3)4] (4) (PPh3= triphenylphosphine). Spectroscopic characterization was carried out using IR, UV-Visible and NMR techniques and confirmed by single crystal X-ray diffraction. In each complex a singular coordination mode for the thiosaccharinate ligand is observed. The most important features of the different coordination modes of the thionates are discussed. Compound 3 crystallizes in monoclinic system, space group Pn, with a = 11.2293(3) Å, b = 12.7282(3) Å, c = 13.6056(4) Å, β = 94.985(2)°, Z = 2; while crystals of compound 4 are monoclinic, space group P21/n, a = 15.024(3) Å, b = 14.681(3) Å, c = 21.914(4) Å, β = 95.31(3)°, Z = 2. The coordination around the silver atoms in both complexes consists of almost trigonal-planar arrangements, AgP2S in 3 and AgS2P in 4.