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Synthesis and structural characterization of six pentanuclear and tetranuclear Mo/W-Cu-S clusters with BIS(Diphenylphosphanyl) methane

Six heterothiometalic clusters, namely,[WS4Cu4(dppm)4]-(ClO4)2?2DMF?MeCN (1), [MoS4Cu4(dppm)4](NO3)2?MeCN (2) [MoS4Cu3(dppm)3](ClO4)?4H2O (3), [WS4Cu3(dppm)3](NO3)?4H2O (4), [WS4Cu3(dppm)3]SCN?CH2Cl2 (5), and [WS4Cu3(dppm)3]I?CH2Cl2 (6) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1?4 were obtained by the reactions of (NH4)2MS4 (M = Mo, W) with [Cu2(mu2-dppm)2(MeCN)2(ClO4)2] {or [Cu(dppm)(NO3)]2} in the presence of 1,10-phen in mixed solvent (CH3CN/CH2Cl2/DMF for 1 and 2, CH2Cl2/CH3OH/DMF for 3 and 4. Compounds 5 and 6 were obtained by one-pot reactions of (NH4)2WS4 with dppm and CuSCN (or CuI) in CH2Cl2/CH3OH. These clusters were characterized by single-crystal X-ray diffraction as well as IR,1H NMR, and31P NMR spectroscopy. Structure analysis showed that compounds 1 and 2 are ?saddle-shaped? pentanuclear cationic clusters, whereas compounds 3?6 are ?flywheel-shaped? tetranuclear cationic clusters. In 1 and 2, the MS42- unit (M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3?6, the MS42- unit is coordinated by three copper atoms and each copper atom is bridged by three dppm ligands.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”