FORMATION AND X-RAY STRUCTURE OF A NOVEL TETRADECANUCLEAR SILVER CLUSTER COMPLEX, )(PPH(3))(8)CENTER-DOT-4CH(3)OH-CENTER-DOT-13H(2)O

A neutral tetradecanuclear silver thiolate complex has been formed fro m the reaction of (Ph(3)P)(2)Ag(S(2)CSPh) with CH2Cl2 and MeOH, and st ructurally characterized by X-ray diffraction analysis. The core of th e cluster [Ag-14(mu(6)-S)(SPh)(12)(PPh(3))(8)] contains an Ag14S12 cag e composed of staggered Ag-6, Ag-8, S-12 polyhedra. There is a mu(6)-s ulfur atom at the centre of the cage, which is weakly bonded to six si lver atoms of an Ag-6 octahedron. Eight terminal PPh(3) ligands are co ordinated to the other eight silver atoms, which form an Ag-8 cube. Tw elve S atoms of a S-12 icosahedron bridge the Ag-6 and Ag-8 polyhedra.