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化学学报
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化学学报 ›› 1987, Vol. 45 ›› Issue (3): 213-219.    下一篇

研究论文

具有局部松散配位的三核钼簇合物研究:{Mo3(μ3-S)(μ-S)3[S2P(OEt)2]4.P(C6H5)3}.(O86CH2Cl2)的合成和晶体结构

黄建全;卢绍芳;林玉辉;黄金陵;卢嘉锡   

  1. 中国科学院福建物质结构研究所
  • 发布日期:1987-03-15

Research on partially "loosely" coordinated trinuclear molybdenum cluster compounds: The synthesis and crystal structure of {Mo3(\m-S)(\m-S)3[S2P(OEt)2]4.P(C6H5)3}.(0.86CH2Cl2)

HUANG JIANQUAN;LU SHAOFANG;LIN YUHUI;HUANG JINLING;LU JIAXI   

  • Published:1987-03-15

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本文报道了具有局部松散配位的三核钼原子簇{Mo3(μ3-S)(μ-S)[S2P(OEt)2]4.P(C6H5)3}.(0.86CH2Cl2)的合成和晶体结构.在CAD-4四圆衍射仪上用Mo Kα射线收集到I≥2σ(I)的衍射点4840个.采用重原子法和差电子密度法解出结构,并用全矩阵最小二乘法修正,最终偏离因子为0.058.簇分子的Mo-Mo键为2.731(1),2.748(1),2.753(1)A,Mo原子和三苯基膦的P原子配位键长为Mo-P2.647(3)A,显著长于一般的Mo-P共价单键.三苯基膦基团在Mo的配位多面体中处于三重桥S原子的对位,表现出与其他此类簇合物的松散配位体配位位置不同.文中概括了此类簇合物的Mo-Mo键和Mo-L的成键情况.

关键词: 晶体结构测定, 红外分光光度法, 质子磁共振谱法, 磁导率, 钼络合物, 三苯基膦, 化学键, 簇状化合物, 磷酸酯类, 多核络合物

The synthesis and crystal structure of the title trinuclear Mo cluster compound with somewhat loose coordination sites are reported. The compound is triclinic, space group P1, with a 10.472(4), b 14.375(2), c 21.695(3) ? a 74.04(1), b 76.50(2), and g 72.22(2)? d.(calcd.) = 1.693 for Z = 2. The atomic parameters are given. The structure was solved by the heavy-atom method and refined by full-matrix least-squares to R = 0.058. The distances between Mo atoms in this cluster are 2.731(1), 2.748(1), and 2.753(1) ? The mean value of Mo-Mo bond lengths is slightly shorter than those found in other trinuclear Mo clusters with a "loosely coordinated" site. In addition, the PPh3 ligand is loosely coordinated to 1 Mo atom in direction opposite to the m3-S atom with Mo-P bond length of 2.647(3) ? This differs from those of the other structurally analogous clusters, in which the loosely coordinated ligand is trans to m2-S atom. A review of Mo-Mo, Mo-L bonding for such clusters is given.

Key words: CRYSTAL STRUCTURE DETERMINATION, INFRARED SPECTROPHOTOMETRY, PROTON MAGNETIC RESONANCE SPECTROMETRY, MAGNETIC PERMEABILITY, MOLYBDENUM COMPLEX, TRIPHENYLPHOSPHINE, CHEMICAL BONDS, CLUSTER COMPOUND, PHOSPHORIC ACID ESTER, POLYNUCLEAR COMPLEX

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