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Synthesis and Structural Characterization of Six Pentanuclear and Tetranuclear Mo/W‐Cu‐S Clusters with Bis(diphenylphosphanyl) Methane
Author(s) -
Li Zhongfeng,
Li Jianbao,
Fan Weiwei,
Xue Xiaonan,
Wang Rong,
Jiang Yuhan,
Wu Manhua,
Jin Qionghua
Publication year - 2014
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201400151
Subject(s) - cationic polymerization , chemistry , crystallography , crystal structure , molecule , nuclear magnetic resonance spectroscopy , single crystal , solvent , stereochemistry , medicinal chemistry , polymer chemistry , organic chemistry
Abstract Six heterothiometalic clusters, namely, [WS 4 Cu 4 (dppm) 4 ](ClO 4 ) 2 · 2DMF · MeCN ( 1 ), [MoS 4 Cu 4 (dppm) 4 ](NO 3 ) 2 · MeCN ( 2 ) [MoS 4 Cu 3 (dppm) 3 ](ClO 4 ) · 4H 2 O ( 3 ), [WS 4 Cu 3 (dppm) 3 ](NO 3 ) · 4H 2 O ( 4 ), [WS 4 Cu 3 (dppm) 3 ]SCN · CH 2 Cl 2 ( 5 ), and [WS 4 Cu 3 (dppm) 3 ]I · CH 2 Cl 2 ( 6 ) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1 – 4 were obtained by the reactions of (NH 4 ) 2 M S 4 ( M = Mo, W) with [Cu 2 (μ 2 ‐dppm) 2 (MeCN) 2 (ClO 4 ) 2 ] {or [Cu(dppm)(NO 3 )] 2 } in the presence of 1,10‐phen in mixed solvent (CH 3 CN/CH 2 Cl 2 /DMF for 1 and 2 , CH 2 Cl 2 /CH 3 OH/DMF for 3 and 4 . Compounds 5 and 6 were obtained by one‐pot reactions of (NH 4 ) 2 WS 4 with dppm and CuSCN (or CuI) in CH 2 Cl 2 /CH 3 OH. These clusters were characterized by single‐crystal X‐ray diffraction as well as IR, 1 H NMR, and 31 P 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 M S 4 2– unit ( M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3 – 6 , the MS 4 2– unit is coordinated by three copper atoms and each copper atom is bridged by three dppm ligands.