高等学校化学学报

高等学校化学学报 ›› 1988, Vol. 9 ›› Issue (7): 651.

• 论文 • 上一篇    下一篇

钨的原子簇化合物研究(Ⅰ)——九氯二钨酸盐的EXAFS和单晶结构分析

吕冈, 陈民勤, 马礼敦, 金松林, 顾翼东   

  1. 复旦大学
  • 收稿日期:1986-12-31 出版日期:1988-07-24 发布日期:1988-07-24
  • 通讯作者: 吕冈

Studies on Tungsten Cluster Compounds(Ⅰ)——Structural Determination of M3W2CI9 by EXAFS and Single Crystal Diffraction

Lu Gang, Chen Minqin, Ma Lidun, Jin Songlin, Gu Yidong   

  1. Fudan University, Shanghai
  • Received:1986-12-31 Online:1988-07-24 Published:1988-07-24

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摘要： 在实验室转靶EXAFS装置上测定了钨原子簇化合物K3W2Cl9,(NHD4)3W2Cl9,(Bu4N)3W2Cl9的阴离子结构.在ENRAF-NONIUSCAD-4四圆单晶衍射仪上测定了(NH4)3W2Cl9的晶体结构。在实验误差范围内,W2Cl93-结构的EXAFS结果与单晶结果符合较好。实验结果表明,在与不同的一价阳离子结合时,阴离子W2Cl93-仍保持双共面八面体的结构。由于其中强烈的W—W金属多重键结合,使得整个阴离子的骨架和键长都没有显著变化。

关键词: 九氯二钨酸盐, EXAFS

Abstract: EXAFS measurements were performed on a 12-kWrotating anode X-ray spectrometer for K3W2Cl9, (NH4)3 W2Cl9 and (Bu4N)3W2Cl9. Through Fourier transformation and curve fitting processes, the bond lengths and coordination numbers were obtained. W-W 2.43(1) Å, CN 1, W-Clt 2.44(3) Å, CN 3.3; W- Clb2.49(3)Å, CN 3.8. In order to certify the EXAFSresults, the single crystal structure of (NH4)3W2Cl9 was determined on ENRAF-NONIUS CAD-4 four-circle X-ray diffractometer. (NH4)3W2Cl9 crystallizes in space group P6θ/m and contains two formula unit in a unit cell, a = 6 = 7.216Å, c=16.518Å, dc = 3.303g/cm3. Within experimental error, the structural parameters of W,Cl93- determined by EXAFS technique are in good agreements with those by single crystal diffraction. It is infered that, combined with +1 cations, the anion W2Cl93- has the structure of two octahedra sharing a face to give D3d symmetry, and the skeleton and bond lengths have no tremendous change due to the strong W—W multi-bond.

Key words: W2Cl93- compounds, EXAFS

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