[Mo12S12O12(OH)12(H2O)6]: A Cyclic Molecular Cluster Based on the [Mo2S2O2]2+ Building Block

The pH-dependent self-condensation of the [Mo ₂ S ₂ O ₂ ] ²⁺ complex fragment gives the wheellike Mo₁₂ cluster depicted on the right (ball-and-stick model; large balls: S, medium balls: O, small balls: Mo). Applying this synthetic strategy to other starting materials could provide access to other polyoxothiometalates with well-defined cavities.     

4:2钼、钨过氧配合物的制备、结构及其氧化还原分解行为

本文作者曾在用过钨酸分解法制备钨酸的过程中发现, 溶液中W与O2^2^-之比始终为2:1, 这一事实说明溶液中有2:1金属过氧配合物形成, 2:1铂过氧络合物[Mo4O12(O2)2]^4^-文献上已有记载, 但类似的钨配合物尚未见报道。本文制备了这二种配合物, 对比它们的红外和Raman光谱, 并用循环伏安法, 恒电位电解法探讨它们的氧化还原分解体系。     

4:2钼, 钨过氧配合物的热稳定性研究

用热分析、程序升温超高真空质谱、真空原红外光谱等技术研究属于VskaIIb4:2钼、钨过氧配合物K~4M~4O~1~2(O~2)~1、K~4W~4O~1~2(O~2)~2.4H~2O的热分解行为, 前者中两个过氧基同时分解(278℃), 后者分两步进行(180和342℃), 每步分解一个过氧基, 4:2钨过氧配合物出现在180℃分解的原因是由于结晶水的作用。比较钼、钨过氧配合物分解温度, 发现VaskaIIb型配合物的热稳定性都比VaskaIIa 型的高。     

Cluster complexes [Mo3O2S2(Acac)3(Amine)3]PF6

New mixed-ligand cluster complexes [Mo₃O₂S₂(Acac)₃(Amine)₃]PF₆ (Amine = morpholine (Mor), 4-cyanopyridine (PyCN), pyrazine (Pz)) have been synthesized. The compounds were characterized by IR spectroscopy and mass spectrometry (ESI-MS). The crystal structure of the Mor complex, which was isolated as [Mo₃(μ₃-S)(μ₂-O)₂(μ₂-S)(Acac)₃(Mor)₃]PF₆ · 0.5Mor · 0.3(CH₃)₂CO was determined. The stability of the complexes in methanolic solutions decreases in a row: Mor > PyCN > Pz.     

Thermal Decomposition of (NH4)2[Mo3S(S2)6] · nH2O

The thermal decomposition of (NH₄)₂[Mo₃S(S₂)₆] · nH₂O was studied by DTA/TG, infrared spectroscopy, X-ray diffraction, determination of specific surfaces and temperature programmed desorption measurements. The results are reported and discussed with respect to the stability of the Mo^IV-triangle system which is retained during the thermal treatment up to the formation of hexagonal MoS₂, which can be understood nicely from a mechanistic point of view.     

[(CH_3)_4N]_2Na[Mo_2O(S_2)_3S_5]·H_2O的合成和晶体结构

标题晶体属斜方晶系,空间群Pbn2_1,a=9.086(2),b=13.439(3),c=22.858(11),V=2791,Z=4,Dc=1.927g/cm~3。在CAD—4衍射仪上收集强度数据,采用直接法和Fourier技术解出结构,并用全矩降最小二乘法修正。对于1180个独立衍射最终偏离因子0.067。结构中的阴离子与其同系物[(CH_3)_4-N]_2K(Mo_2O(S_2)_3(NO)_2]·H_2O中的阴离子配位情况相似。只是结构中的Mo—S与Mo—O键长有差异。这种差异在两者的红外光谱上有着相应的表现。     

On the studies of the vibrational spectra of cluster [Mo2O2S2(S2)2]2-

IR and Raman spectra of [Mo₂O₂S₂(S₂)₂]^2- were reported. The resonance Raman spectra and the depolarization ratios in CH₃CN solution were measured. By using the data of crystal structure, the simplified normal coordinate calculation of the stretching vibrations for anion [Mo₂O₂S₂(S₂)₂]^2- was performed. The results obtained are useful to assign the vibrational bands of some Mo-Fe-S clusters.     

Studies of molybdenum thiolato-complexes. The crystal and molecular structures of two triply bridged Mo(V) dimers, [Bu 4 n N][Mo2O2Cl5(SPh)2] and [Mo2O3(SPh)2(S2CNMe2)2]

Summary The complex [Bu ₄ ⁿ N][Mo₂O₂Cl₅(SPh)₂] has been prepared by reaction of [Bu ₄ ⁿ N][MoO(SPh)₄] with stoichiometric amounts of HCl and characterised by single crystal X-ray structure analysis. The dimer is bridged by two oxo-groups and one chloride and each Mo has pseudo-octahedral co-ordination. The related compound [Mo₂O₃(SPh)₂(S₂CNMe₂)₂] was synthesised by reaction of [MoO₂(S₂CNMe₂)₂] with thiophenol in methanol and has also been characterised crystallographically. In this case the triple-bridge consists of two thiophenolate sulphurs and one oxo-group, each molybdenum having pseudo-octahedral geometry. These structures are compared with other triply-bridged species.     

K2[Mo2O4(C2O4)2(H2O)2]·3H2O

The crystal and molecular structure of dipotassium di‐μ‐oxo‐bis[aqua(oxalato‐O¹,O²)oxomolybdenum(III)] trihydrate, K₂­[Mo₂O₄(C₂O₄)₂(H₂O)₂]·3H₂O, has been determined from X‐ray diffraction data. In the dimeric anion, which has approximate twofold symmetry, each Mo atom is in a distorted octahedral coordination, being bonded to one terminal oxo‐O atom, two bridging O atoms, two O atoms from the oxalato ligand and one from the water mol­ecule. Bond lengths trans to the multiple‐bonded terminal oxo ligand are larger than those in the cis position, confirming the trans influence as a generally valid rule.     

Structures of novel R(2)Mo(5)O(18) and R(6)Mo(12)O(45) (R = Eu and Gd) prepared by thermal decomposition of polyoxomolybdate precursor [R2(H2O)(12)Mo(8)O(27)].nH2O

Single crystals of R(2)Mo(5)O(18) and R(6)Mo(12)O(45) (R = Eu and Gd), which are novel compounds in the R(2)O(3)-MoO(3) system, have been obtained by thermal decomposition of [R(2)(H(2)O)(12)Mo(8)O(27)].nH(2)O in air at 750 degrees C for 2 h. TG-DTA and X-ray diffractometry showed that R(2)Mo(5)O(18) crystallizes in a melt of the dehydrated precursor (R(2)Mo(8)O(27)), and R(2)Mo(5)O(18) is transformed to R(6)Mo(12)O(45) in the solid state, both occurring with the loss of MoO(3). R(2)Mo(5)O(18) species crystallize isostructurallyas orthorhombic, Pbcn, Z = 4, with lattice constants of a = 19.2612(7) and 19.246(1) A, b = 9.4618(3) and 9.4414(5) A, c = 9.3779(3) and 9.3446(4) A for R = Eu and Gd, respectively. R(6)Mo(12)O(45) crystallize isostructurally as triclinic P1, Z = 1, with lattice constants of a = 9.3867(4) and 9.3409(3) A, b = 10.9408(5) and 10.8826(5) A, c = 11.4817(5) and 11.4377(5) A, alpha = 104.194(2) degrees and 104.170(1) degrees, beta = 109.567(3) degrees and 109.288(4) degrees, gamma = 108.998(2) degrees and 109.266(2) degrees for R = Eu and Gd, respectively. Both structures consist of [RO(8)] square-antiprisms and [MoO(n)] polyhedra. In R(2)Mo(5)O(18), an [RO(8)] polyhedron is attached by only molybdate groups, being isolated from adjacent [RO(8)] groups. The 12 nearest R atoms surrounding an R atom with R...R distances of 6.0735(4)-7.0389(4) A form an approximate cuboctahedron. All the [RO(8)] square-antiprisms in R(6)Mo(12)O(45) are connected to each other by face-sharing to form dimeric [R(2)O(13)] and [R(2)O(12)] groups. The latter unusual [R(2)O(12)] group is achieved by sharing a square-face via four bridging O atoms with a very short R...R separation (3.4741(7) and 3.4502(6) A for R = Eu and Gd, respectively).     

从固相反应产物[NEt4]4[Mo2O2S6Cu6I4Br2]合成原子簇[MoOS3Cu3I(3,5-diMePy)4]·CH3CN和(EtN)4[Mo4Cu8O4S12{(Ph2PS)2}4](英文)

Treatment of iodide-bridged dimer [NEt4] 4[Mo2O2S6Cu6I4Br2] 1 with 3, 5-bimethylpyridine or with K[(Ph2PS) 2N] in CH3CN afforded the tetranuclear cluster [MoOS3Cu3I(3,5-diMePy)4]·CH3CN 2 and dodecanuclear cluster (Et4N)4[Mo4Cu8O4S12{(Ph2PS)2N}4] 3. Monomeric 2 possess a nest-shaped skeleton.The structure of oligomeric 3 can be regarded as a tetramer of nest-shaped MoCu3OS3[(Ph2PS)aN]groups co-polymerized by sharing the limbic Cu atoms.     

簇合物[Et4N]2[Mo2S4(SCH2CH2S)2]的合成及晶体结构

以(NH4)2MoS4,Et4NBr,HSCH2CH2SH为原料合成了新的簇合物——[Et4N]2[Mo2S4(SCH2CH2S)2],其结构经X射线四圆衍射仪,IR。UV及元素分析确证。其晶体属单斜晶系。晶胞参数为：a=1．0304(8)nm,b=1．4158(8)sin。c=1．1417(1)nm,V=1．63801nm^3,z=4。晶体结构经块状矩阵最小二乘法修正后,最终偏离因子R=0．084。