Formation and X-ray structure of a novel tetradecanuclear silver cluster complex, Ag-14(mu(6)-S)(SPh)(12)(PPh(3))(8)center dot 4CH(3)OH center dot 13H(2)O

A neutral tetradecanuclear silver thiolate complex has been formed from the reaction of (Ph(3)P)(2)Ag(S(2)CSPh) with CH2Cl2 and MeOH, and structurally characterized by X-ray diffraction analysis. The core of the cluster [Ag-14(mu(6)-S)(SPh)(12)(PPh(3))(8)] contains an Ag14S12 cage composed of staggered Ag-6, Ag-8, S-12 polyhedra. There is a mu(6)-sulfur atom at the centre of the cage, which is weakly bonded to six silver atoms of an Ag-6 octahedron. Eight terminal PPh(3) ligands are coordinated to the other eight silver atoms, which form an Ag-8 cube. Twelve S atoms of a S-12 icosahedron bridge the Ag-6 and Ag-8 polyhedra.