Synthesis and Structural Characterization of Six Pentanuclear and Tetranuclear Mo/W‐Cu‐S Clusters with Bis(diphenylphosphanyl) Methane |
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| Authors: | Zhongfeng Li Jianbao Li Weiwei Fan Xiaonan Xue Rong Wang Yuhan Jiang Manhua Wu Qionghua Jin |
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| Institution: | Department of Chemistry, Capital Normal University, 100048 Beijing, China |
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| Abstract: | 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(μ2‐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, and 31P 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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| Keywords: | Clusters Bis(diphenylphosphanyl)methane Molybdenum Tungsten Copper |
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