三核钼钨簇合物的电化学性质研究

合成了四种三核钼钨簇合物（［Ｍｏ３Ｌ］２＋，［Ｍｏ２ＷＬ］２＋，［ＭｏＷ２Ｌ］２＋，［Ｗ３Ｌ］２＋，其中Ｌ＝［（μ３－Ｏ）２（μ－ＣＨ３ＣＯＯ）６（Ｈ２Ｏ）３］）。并研究了四种簇合物在铂电极上的电化学特性，结果表明：在０．０１ｍｏｌ／Ｌ簇合物的水溶液中，［Ｍｏ３Ｌ］２＋，［Ｍｏ２ＷＬ］２＋出现两个氧化峰，两个还原峰。［Ｗ３Ｌ］２＋，［Ｗ２ＭｏＬ］２＋则出现三个氧化峰和两个还原峰，四种簇合物的电化学性质不同，主要是由于钼钨的外层电子排布不同造成的。

三核钼钨簇合物的循环伏安法研究

本文利用循环伏安法在铂电极上研究了三核钼钨簇合物（〔Ｍｏ３Ｌ〕２＋ ，〔Ｗ ３Ｌ〕２＋其中Ｌ＝ 〔（μ３－ Ｏ）２（μ－ ＣＨ３ＣＯＯ）６（Ｈ２Ｏ）３〕的电化学性质及其对电化学性质的影响因素。

系列异金属类立方烷原子簇化合物的振动光谱

通过振动光谱和X 射线结构分析数据的结合 ,归属了系列具有 [M3 YS3 M′](M =Mo ,W ;Y =O ,S ;M′=Cu ,Sn ,Sb ,Pb ,Bi)簇芯的异金属四核类立方烷原子簇化合物的主要振动谱峰。讨论了五种结构类型的光谱特征和成键状态。M′的加入使νM— (μ3—Y) 和νM S 频率下降。当M′为过渡金属 ,例如Cu时 ,Cu与[M3 YS3 ]结合紧密造成了与Cu—S共价键相当的νCu—S振动频率。而当M′为主族金属时 ,νM′—S远小于相应共价键的振动频率值。文中还对νM—M 振动进行若干论述。

计算机辅助化学研究——MoWS:Mo—S、W—S原子簇化合物的合成和表征

1.引言计算机在化学化工中应用的早期工作主要是用计算机进行一些化学化工中的数值计算。六十年代中期,化学家们开始将计算机应用于非数值运算领域。随着计算机科学和技术的发展,特别是价格便宜的各种微型计算机的普及,计算机辅助教学CAI(ComputerAssisted Instruction)的研究日益活跃。

Synthesis and Structure of Propionate-bridged Mixed-metal Cluster Compound: MoW_2O_2 (O_2CC_2H_5)_6 (H_2O)_3 ZnBr_4·4H_2O

The heterotrinuclear cluster compound [MoW_2O_2 (O_2CC_2H_5 )_6-( H_2O)_3] ZnBr4·4H_2O was prepared by the redox reaction of Mo (CO)_6 with Na_2W_O4 in propionic anhydride. The crystal is monoclinic of space group P2/c with a =16. 334(4) , b= 9. 657(5) , c=19. 889(9) ,β= 139. 79 (5)°,V= 2026 (2) ￣3 , Z=2 , D_c=2. 30 g/cm￣3 μ(MoKa) =106. 6 cm￣(-1) ,F(000)=1176 ,final R=0. 065 and R_ω=0. 072 for 1964 reflections with I≥3σ(I). In the structure of cation [MoW_2O_2 (O_2CC_2H_5 )_6 (H_2O)_3]￣(2+) molybdenum and tungsten atoms are statistically disordered. Three metal atoms form an equilateral triangle with the distance of M-M being 2. 735.

Electrochemical Study of Trinuclear Metal Complexes ［M_3O_2（O_2CCH_3）_6（H_2O）_3］^（2＋）（M_3＝Mo_3，MoW_2，W_3）

In this paper detailed studies of the cyclic voltammetry(CV) of trinuclear metal cluster compounds [M_3O_2(O_2CCH_3,)6(H,O),j z+ (M,=Mo3,MoW2,W3) are reported.The result of CV shows that they are similar to each other.There are a reversible redox peak near-0. 48 V and an irreversible reduced peak near-1.10 V in the scan range of + l.0 V to l. 5 V.It implies that the M_3O_2,clusters might gain one electron to be further reduced.But the two-electron-reduced product of M_3O_2 clusters are instable.The theoretical calculations(EHMO) agree well with the result of the CV experiment.

Synthesis and Crystal Structure of Mixed Mo-W Cubane-type Cluster Compound [Mo_2W_2S_4 (μ-OAc)_2 (dtp)_3(dtpH)]·CH_2Cl_2

The cubane-type mixed Mo W cluster[Mo2W2S4 (OAc)2(dtp)3 (dtpH)]·CH2Cl2 (dtp= (EtO)2PS2, dtpH = (EtO)2PS (SH) has been prepared by reduction and addition reaction between dinuclear W2S4 (dtp)2 and Mo(CO)6 in HOAc and Ac2O solution in the presence of dtp-ligand. Crystallographic data: Mr=1632. 71,monoclinic, space group P2/n, a=13. 146 (8), b=11. 961 (5),c=17. 157 (9) β =105. 99(8)°, V=2593(8), Z=2, Dc=2. 09 /cm￣3 ,λ(MoKa) =0.71073 ,F (000)=1578, final R=0. 029, Rw = 0. 041 for 3765 unique intensity data [I≥4σ (I)]. The result of X-ray study and elemental analysis indicated that, in the crystal lattice, molybdenum and tungsten are statistically distributed in the metal positions each with 0. 5 fractional occupation.

MULTIPLE CENTER d-β ORBITALS AND CHARGE TRANSFER OF HETERONUCLEAR COUSTERS WITH CUBANE TYPE (Mo_3S_4)_xM^n+ (x=1, 2, M = Cu, W, Ni, Sb. Mo, Sn, Cu_2; n = 4,8)

In this work, with the analysis on MO and electronic structure for a series of heteronuclear cluster with cubane type (Mo4S1 )xMn1(x=1.2. M = Cu, W, Ni, Sb, Mo, Sn, Cu2) we found that it is with the multiple center d-pir orbitals that the ligand Mo3S44+ bonds to the M atom to form these class clusters. It is revealed that the charges transfer from the M atom to Mo atom of the ligand Mo3S44+ and its relationship with the MC (multiple center) d-pπ orbitals. Based on the charge transfer the electronic spectrum and the magnetic property of some cubane clusters have been discussed.