Syntheses and Characterizations of a Series of Tetradecanuclear Molybdenum(Tungsten)/Copper/Sulfur Heterobimetallic Cluster Compounds
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- 作者：Jun Guo ; Tianlu Sheng ; Wenjian Zhang ; Xintao Wu ; Ping Lin ; Quanming Wang ; and Jiaxi Lu
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：July 27, 1998
- 年：1998
- 卷：37
- 期：15
- 页码：3689 - 3697
- 全文大小：143K
- 年卷期：v.37,no.15(July 27, 1998)
- ISSN：1520-510X
文摘
Using sulfide ion to substitute the weakly copper(I)-philic ligands of MS4-n2-On/Cu+ compounds, (M = Mo, W;n = 0, 1), we have prepared and characterized four novel tetradecanuclear clusters having the general formula[(n-Bu)4N]4[M4Cu10S16E2E']H2O, (M = Mo, E = E' = O for complex 1; M = W, E = 1/2O + 1/2S, E' = O, forcomplex 2; M = Mo, E = S, E' = 1/2O + 1/2S for complex 3; M = W, E = E' = S, for complex 4). Crystalstructures of compounds 1-4 were determined; they are isomorphous and crystallized in the orthorhombic spacegroup Pna21, with a = 26.6997(2) Å, b = 19.3133(4) Å, c = 21.4577(4) Å, V = 11064.9(3) Å3, Z = 4 for[(n-Bu)4N]4[Mo4Cu10S18O]·H2O (3) and with a = 26.8141(8) Å, b = 19.4412(6) Å, c = 21.4039(5) Å, V =11157.8(5) Å3, Z = 4 for [(n-Bu)4N]4[W4Cu10S19]·H2O (4). The cluster cores have approximate 
symmetry.The anions 1-4 may be viewed as consisting of one incomplete cubane-like Cu3MS3E fragment, one trigonalprism-type Cu3MS4, and two butterfly-type Cu2MS3E' fragments, bridged by two 
3-S and one 4-S atoms. Thereare two (3-S)Cu3 configurations in the compounds. Infrared, Raman, and UV/vis spectra of the above compoundsare discussed, and the main absorption bands are assigned. 95Mo NMR spectra and cylic voltammograms areinvestigated and compared with those of other compounds, 95Mo NMR spectra show that in the solution there arethree kinds of coordination environments of Mo in complexes 1 and 3, and cyclic voltammograms indicate thatcomplexes 1-4 have irreversible electrochemical reductions.
symmetry.The anions 1-4 may be viewed as consisting of one incomplete cubane-like Cu3MS3E fragment, one trigonalprism-type Cu3MS4, and two butterfly-type Cu2MS3E' fragments, bridged by two 3-S and one 4-S atoms. Thereare two (3-S)Cu3 configurations in the compounds. Infrared, Raman, and UV/vis spectra of the above compoundsare discussed, and the main absorption bands are assigned. 95Mo NMR spectra and cylic voltammograms areinvestigated and compared with those of other compounds, 95Mo NMR spectra show that in the solution there arethree kinds of coordination environments of Mo in complexes 1 and 3, and cyclic voltammograms indicate thatcomplexes 1-4 have irreversible electrochemical reductions.