Synthesis And Crystal Structure Of Mo(W)/Cu/S Cluster Compounds

In the past thirty years, synthesis and characterization of heteronuclear metal sulfide clusters from thiometallates [MOnS4-n]m- (M = Mo, W, V, Re, Nb, Ta; n = 0-3; m = 1-3) remains a subject of intense interest due to their rich structural diversity, their relevance to biological systems, industrially important catalytic process, and their potential utility as optoelectronic materials.This thesis reported isolation of five novel Mo(W)/Cu/S clusters through reactions of (NH4)2[MS4] (M = Mo, W) with various Cu(I) salts or complexes. They are [(n-Bu)4N]3[MoS4Cu5Br6] (1); [MoS4Cu4(dppm)4](NCS)2-4(CH3)2CHOH (2); [WS4Cu4(dppm)4][Cu(NCS)4] (3); [(n-Bu)4N]4[(MS4)4Cu4] (4: M = Mo; 5: M = W). Clusters 1-5 have been characterized by elemental analysis, and IR spectra, and the crystal structure of 1-3 have been determined by X-ray crystallography. The structure of the [MoS4Cu5Br6]3- trianion of 1 is composed of one nido-like [M0S3CU3] fragment and one half-open cubane-like [MoS3Cu3Br] fragment, which are interconnected by sharing the same MoSCuS plane. The structure of the dication of 2 or 3 may be described as being a "host-guest" structure in which an MS4 unit is surrounded by a sixteen-membered [-Cu-P-C-P-]4 ring.The synthesis and structural characterization of 1-5 not only rich the structural chemistry of Mo(W)/Cu/S cluster compounds, but also offer more choices for screening out the better non-linear optical cluster materials.