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  

Studies on Tungsten Cluster Compounds(Ⅰ)——Structural Determination of M_(3)W_(2)CI_(9) by EXAFS and Single Crystal Diffraction

作　　者：吕冈 陈民勤[1] 马礼敦[1] 金松林[1] 顾翼东[1] Lu Gang;Chen Minqin;Ma Lidun;Jin Songlin;Gu Yidong(Fucian University,Shanghai)

机构地区：[1]复旦大学

出　　处：《高等学校化学学报》1988年第7期651-655,共5页Chemical Journal of Chinese Universities

摘　　要：在实验室转靶EXAFS装置上测定了钨原子簇化合物K_(3)W_(2)Cl_(9),(NHD_(4))_(3)W_(2)Cl_(9),(Bu_(4)N)_(3)W_(2)Cl_(9)的阴离子结构.在ENRAF-NONIUS CAD-4四圆单晶衍射仪上测定了(NH4)3W 2Cl9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。EXAFS measurements were performed on a 12-kW rotating anode X-ray spectrometer for K_(3)W_(2)Cl_(9),(NH_(4))_(3)W_(2)Cl_(9) and(Bu_(4)N)_(3)W_(2)Cl_(9).Through Fourier transformation and curve fitting processes,the bond lengths and coordination numbers were obtained.W-W 2.43(1)A,CN 1,W-Clt 2.44(3)A,CN 3.3;W-Clb 2.49(3)A,CN 3.8.In order to certify the EXAFS results,the single crystal structure of(NH4)3W2Cl9 was determined on ENRAF-NONIUS CAD-4 four-circle X-ray diffractometer.(NH_(4))_(3)W_(2)Cl_(9) crystallizes in space group P68/m and contains two formula unit in a unit cell,a=6=7.216A,c=16.518A,dc=3.303g/cm^(3).Within experimental error,the structural parameters of W,C193-determined by EXAFS technique are in good agreements with those by single crystal diffraction.It is infered that,combined with+1 cations,the anion W_(2)Cl_(9)^(3-)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.

关 键 词：九氯二钨酸盐 EXAFS 

分 类 号：O64[理学—物理化学]