Syntheses and characterization of cubane-type clusters, [Mo4S4(edta)2]n− (n=2–4), [Mo4S4(H2O)12]n+ (n=4–6) and [Mo4S4(NH3)12]4+. X-ray structures of Na2[Mo4S4(edta)2]·6H2O, Ca1.5[Mo4S4(edta)2]·13H2O, Mg2[Mo4S4(edta)2]·2OH2O, [MO4S4(H2O)12](CH3C6H4SO3)5·14H2O and [MO4S4(NH3)12]Cl4·7H2O
Syntheses and characterization of cubane-type clusters, [Mo4S4(edta)2]n− (n=2–4), [Mo4S4(H2O)12]n+ (n=4–6) and [Mo4S4(NH3)12]4+. X-ray structures of Na2[Mo4S4(edta)2]·6H2O, Ca1.5[Mo4S4(edta)2]·13H2O, Mg2[Mo4S4(edta)2]·2OH2O, [MO4S4(H2O)12](CH3C6H4SO3)5·14H2O and [MO4S4(NH3)12]Cl4·7H2O
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立方烷型簇的合成和表征，[Mo4S4(edta)2]n− (n=2–4)、[Mo4S4(H2O)12]n+ (n=4–6) 和 [Mo4S4(NH3)12]4 +. CH3C6H4SO3)5·14H2O 和 [MO4S4(NH3)12]Cl4·7H2O
DOI：
10.1016/s0020-1693(00)92332-6
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发表时间：
1993
影响因子：
2.8
通讯作者：
Ooi Shun'ichiro
中科院分区：
文献类型：
--
作者：
Shibahara Takashi;Kuroya Hisao;Akashi Haruo;Matsumoto Keiji;Ooi Shun'ichiro
硫桥式立方体型钼团簇[mo4s4 (edta) 2] 3−(1B)、[mo4s4 (h2o) 12] 5+(2B)和[mo4s4 (nh3) 12] 4+(4C)分别从[mo2s2 (edta) 2−和NaBH 4、mo2s22 +(aq)和NaBH 4、2B和氨水中得到。分离并表征了1B [mo4s4 (edta) 2] n−（n= 4 （1C）和2 (1A)）和2B [mo4s4 (h2o) 12] n+ （n= 4 （2C）和6 (2A)）的还原和氧化形式。团簇1B和2B显示出两个准可逆的单电子波。得到的晶体形貌结果如下：Na 2 [Mo 4 S 4 (edta) 2]·6h2o (Na1A)，单斜，P2 1/n, a= 25.171 (4), b= 11.231 (3), c= 13.417 (3) Å， β= 98.28(1)°，V= 3753.4 （15） Å 3， Z= 4， R= 4.41%；Ca 1.5 [Mo 4 S 4 (edta) 2]·13h2o (Ca1B)，单斜，P2 1/c, a= 15.726 (8), b= 12.447 (4), c= 28.10 (2) Å， β= 123.16(3)°，V= 4604.6 （43） Å 3， Z= 4， R= 5.53%；mg2 [Mo 4 S 4 (edta) 2]·2OH 2o (Mg1C)，单斜，P2 1/m, a= 14.358 (6), b= 13.680 (6), c= 12.990 (5) Å， β= 96.56(2)·，V= 2534.8 （19） Å 3， Z= 2， R= 4.79%；[Mo 4 S 4 (h2o) 12](ch3 C 6 h4 so3) 5·14h2o (2Bpts)（Hpts=对环萘磺酸），三斜，P 1, a= 16.352 (4), b= 16.715 (3), C = 13.109 (4) Å， α= 91.05 (2), β= 98.73 (2), γ= 89.37(2)°，V= 3540.8 （16） Å 3， Z= 2， R= 4.06%；(莫4 S 4 (NH 3), 12] Cl 4·7 h 2 O (4 c”)、三斜1 P = 10.529 (3), b = 17.470 (4), c = 9.967(3),α= 96.74(2),β= 116.26(2),γ= 82.91(2)°,V = 1627.4 (8) 3, Z = 2, R = 4.50%。利用自旋极化离散变分(DV)-Xα方法研究了2A、2B和2C的电子结构。XPS测量得到的Mo3d 3/2和Mo3d 5/2的结合能（eV）分别为：Na1A， 232.7, 229.7；na3 [mo4 s4 (edta) 2]·1OH 2o (Na1B), 232.1, 229.0；Mg1C, 232.1, 229.0；2Bpts, 233.0, 230.0；4c ', 232.1, 228.9。
Sulfur-bridged cubane-type molybdenum clusters,[Mo 4 S 4 (edta) 2] 3−(1B),[Mo 4 S 4 (H 2 O) 12] 5+(2B) and [Mo 4 S 4 (NH 3) 12] 4+(4C), are obtained from [Mo 2 O 2 S 2 (edta)] 2− and NaBH 4, from Mo 2 O 2 S 2 2+(aq) and NaBH 4, and from 2B and ammonia-water, respectively. The reduced and oxidized forms of 1B,[Mo 4 S 4 (edta) 2] n−(n= 4 (1C) and 2 (1A)), and those of 2B,[Mo 4 S 4 (H 2 O) 12] n+ (n= 4 (2C) and 6 (2A)), are isolated and characterized. The clusters 1B and 2B show two quasi-reversible, one-electron waves. The crystallographic results obtained are as follows: Na 2 [Mo 4 S 4 (edta) 2]· 6H 2 O (Na1A), monoclinic, P2 1/n, a= 25.171 (4), b= 11.231 (3), c= 13.417 (3) Å, β= 98.28 (1)°, V= 3753.4 (15) Å 3, Z= 4, R= 4.41%; Ca 1.5 [Mo 4 S 4 (edta) 2]· 13H 2 O (Ca1B), monoclinic, P2 1/c, a= 15.726 (8), b= 12.447 (4), c= 28.10 (2) Å, β= 123.16 (3)°, V= 4604.6 (43) Å 3, Z= 4, R= 5.53%; Mg 2 [Mo 4 S 4 (edta) 2]· 2OH 2 O (Mg1C), monoclinic, P2 1/m, a= 14.358 (6), b= 13.680 (6), c= 12.990 (5) Å, β= 96.56 (2)·, V= 2534.8 (19) Å 3, Z= 2, R= 4.79%;[Mo 4 S 4 (H 2 O) 12](CH 3 C 6 H 4 SO 3) 5· 14H 2 O (2Bpts)(Hpts= paratoluenesulfonic acid), triclinic, P 1, a= 16.352 (4), b= 16.715 (3), c= 13.109 (4) Å, α= 91.05 (2), β= 98.73 (2), γ= 89.37 (2)°, V= 3540.8 (16) Å 3, Z= 2, R= 4.06%;[Mo 4 S 4 (NH 3), 12] Cl 4· 7H 2 O (4C′), triclinic P 1, a= 10.529 (3), b= 17.470 (4), c= 9.967 (3) Å, α= 96.74 (2), β= 116.26 (2), γ= 82.91 (2)°, V= 1627.4 (8) Å 3, Z= 2, R= 4.50%. The electronic structures of 2A, 2B and 2C were investigated using the spin-polarized discrete variational (DV)-Xα method. The binding energies (eV) of Mo3d 3/2 and Mo3d 5/2 obtained by XPS measurements are: Na1A, 232.7, 229.7; Na 3 [Mo 4 S 4 (edta) 2]· 1OH 2 O (Na1B), 232.1, 229.0; Mg1C, 232.1, 229.0; 2Bpts, 233.0, 230.0; 4C′, 232.1, 228.9.