Sulfur-Bridged Cubane-Type Molybdenum-Gallium Clusters with Mo3GaS4n+ (n = 5, 6) Cores. X-ray Structures of [Mo3GaS4(H
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- 作者：Takashi Shibahara ; Syoji Kobayashi ; Naoki Tsuji ; Genta Sakane ; and Minoru Fukuhara
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：April 9, 1997
- 年：1997
- 卷：36
- 期：8
- 页码：1702 - 1706
- 全文大小：172K
- 年卷期：v.36,no.8(April 9, 1997)
- ISSN：1520-510X
文摘
Sulfur-bridged cubane-type molybdenum-gallium clusters[Mo3GaS4(H2O)12]5+(2) and[Mo3GaS4(H2O)12]6+(3)have been synthesized from[Mo3S4(H2O)9]4+(1) and gallium metal and have been isolated as2(pts)5·14H2O(2·pts) and3(pts)6·17H2O(3·pts) (Hpts = p-toluenesulfonic acid),whose structures have been characterized byX-ray crystallography. Crystal data for 3·pts:orthorhombic, space group Pca21, a= 11.188(1) Å, b = 30.936(4) Å, c = 23.987(2) Å, V =8301(2) Å3, Z = 4,Dcalcd = 1.628 g cm-3,Dobsd = 1.63 g cm-3,R (Rw) = 5.8%(6.3%) for 6102 reflections (I >3.0
(I)). Crystal data for2·pts: triclinic, space group P
,a = 16.406(4) Å, b= 16.743(3) Å, c = 13.173(4) Å, 
=90.64
, 
= 98.40(2), 
= 89.32(2),V = 3579.2(14) Å3, Z = 2,Dcalcd= 1.681 g cm-3, Dobsd = 1.68 gcm-3, R (Rw) = 6.7%(10.1%) for 7612 reflections (I >3.0(I)). The Mo-Gadistances (3·pts, 3.60[2] Å;2·pts, 3.52[2] Å) are much longer than thecorresponding Mo-Mo (3·pts,2.679[7]Å; 2·pts, 2.713[3] Å) distances. At lowH+ concentrations, such as 0.5 M HCl, 2 isstable, and at H+ concentrationhigher than 2 M HCl, 2 is oxidized by H+ togive 3 with evolution of hydrogen gas. Chloride ionplays animportant role in the oxidation of 2. Electronicspectra of 3·pts and 2·pts are verysimilar. Peak positions and
values (
max, nm (, M-1cm-1)): 3·pts, 762 (447), 550 (204);2·pts, 760 (404), 548 (205). Thecyclicvoltammogram of 3 shows three reduction processes (thecathodic peak potentials, Epc, are -0.83,-1.20, and-1.74 V, respectively), where the first and second processes arequasi-reversible (the anodic peak potentials,Epa,are -0.55 and -1.00 V, respectively). The reduction current ofeach process is close to 1:1:3.
(I)). Crystal data for2·pts: triclinic, space group P,a = 16.406(4) Å, b= 16.743(3) Å, c = 13.173(4) Å, =90.64, = 98.40(2), = 89.32(2),V = 3579.2(14) Å3, Z = 2,Dcalcd= 1.681 g cm-3, Dobsd = 1.68 gcm-3, R (Rw) = 6.7%(10.1%) for 7612 reflections (I >3.0(I)). The Mo-Gadistances (3·pts, 3.60[2] Å;2·pts, 3.52[2] Å) are much longer than thecorresponding Mo-Mo (3·pts,2.679[7]Å; 2·pts, 2.713[3] Å) distances. At lowH+ concentrations, such as 0.5 M HCl, 2 isstable, and at H+ concentrationhigher than 2 M HCl, 2 is oxidized by H+ togive 3 with evolution of hydrogen gas. Chloride ionplays animportant role in the oxidation of 2. Electronicspectra of 3·pts and 2·pts are verysimilar. Peak positions and values (max, nm (, M-1cm-1)): 3·pts, 762 (447), 550 (204);2·pts, 760 (404), 548 (205). Thecyclicvoltammogram of 3 shows three reduction processes (thecathodic peak potentials, Epc, are -0.83,-1.20, and-1.74 V, respectively), where the first and second processes arequasi-reversible (the anodic peak potentials,Epa,are -0.55 and -1.00 V, respectively). The reduction current ofeach process is close to 1:1:3.