Mono and poly-nuclear Silver(I) complexes with triphenylphosphine. synthesis, spectroscopic and structural characterization of thiosaccharinato-bis(triphenylphosphine)silver(I) and tetrakis{thiosaccharinato(triphenylphosphine)silver(I)}

The reaction of Ag-6(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)z] (3) and [Ag-4(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) angstrom, b = 12.7282(3) angstrom, c = 13.6056(4) angstrom, beta = 94.985(2)degrees, Z = 2; while crystals of compound 4 are monoclinic, space group P2(1)/n, a = 15.024(3) angstrom, b = 14.681(3) angstrom, c = 21.914(4) angstrom, beta= 95.31(3)degrees, Z = 2. The coordination around the silver atoms in both complexes consists of almost trigonal-planar arrangements, AgP2S in 3 and AgS2P in 4.