Synthesis And Characterization Of Sulfur-containing Metal Clusters

In recent years, synthesis of copper-sulfur or silver-sulfur clusters with intriguing structure and special physic/chemical properties has become one of the hot topics in inorganic chemistry mainly due to the ever-increasing findings in the respects of biochemistry and new materials.This thesis reports the preparation of a series of Cu(I)/S or Ag(I)/S clusters through reactions of Cu(I) or Ag(I) salts or complexes with two different types of sulfur-containing ligands. Reactions of (NH4)2[Mo2S12] with CuBr afforded a new cluster [MoS4Cu5Br3(Py)7] (1) while substitution of bromide groups of [PPh4][(5-C5Me5)WS3Cu3Br3(dppm)] with pyridine yielded the other cluster [(5-C5Me5)WS3Cu3Br(Py)3(dppm)](PF6) (2). On the other hand, reactions of new thiolate tabHPF6 with different Ag(I) sources produced four one-dimensional Ag/S clusters {[AgBr2](tabH)}n (3a), {[AgBr2](tab)(NH4)}n (3b), {[Ag2(tab)4](PF6)}n (4) and {[Ag3(tab)4](PF6)3}n (5), one polynuclear Ag/S cluster [Ag14( 6-S)(tab)12(PPh3)8](PF6)12 (6) along with a trisilver cluster [Ag3Br2(dppm)3](PF6) (7). Clusters 1-7 have been characterized by elemental analysis, and IR spectra, and the crystal structure of 1~7 except for 3b have been determined by X-ray crystallography. The molecular structure of 1 is composed of two nido-like MoS3Cu3 fragments, which are interconnected by sharing the MoSCuS plane. The structure of the cation of 2 has an incomplete WS3Cu3 cubane-like framework. Compounds 3a, 4 and 5 exhibit one-dimensional structures. The structure of the dodecacacation of 6 shows a peculiar Ag14S12( 6-S)cage which is composed of an Ag6 octahedron, an Ag8 cube and an S12 icosahedron centred around a 6-sulfur atoms. The cluster of 7 can be described as triangular array of Ag atoms connected by two 3-Br atoms and three -dppm ligands.The successful isolation of 1 and 2 provide us new ways to synthesis newMo(W)/Cu/S clusters. More importantly, the synthesis and structural characterization of 3~7 extend our knowledge about a new family of silver-thiolate clusters.