【摘要】 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）₃[S₂P（OEt）₂]₄·P（C₆H₅）₃}·（0.86CH₂Cl₂）的合成和晶体结构。晶体属三斜晶系,空间群为PI,单胞参数a=10.472（4）,b=14.375（2）,c=21.695（3）A;α=74.04（1）,β=76.50（2）,γ=72.22（2）°,V=2950A³,D_c=1.693g·cm^-3,Z=2.在CAD-4四圆衍射仪上用MoKα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。更多还原

【Abstract】 The Synthesis and crystal structure of a novel trinuclear molybdenum cluster compound with somewhat "loose" coordination site {Mo₃（μ3-S） （μ3-S）₃ [S₂P（OEt）₂]₄·P（C6H₅）₃}·（0.86CH₂Cl₂） have been reported. The cluster crystallizes in the space group PI with two molecules in a unit cell whose dimensions are a=10.472（4）, b= 14.375（2）, c=21.695（3）;α=74.04（1）,β=76.50（2）,γ=72.22（2）°, V=2950A³, D_c=1.693g·cm^-3.On the basis of 4840 independent reflections with I≥2σ（I）, the structure was solved by heavy atom method and Fourier method and refined by full-matrix least-squares technique to a final R=0.058.The distances between Mo atoms in this cluster are 2.731（1）, 2.748（1）, 2.753（1）A respectively. 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 one Mo atom in direction opposite to the μ₃-S atom with Mo-P bond length of 2.647（3）A This differs from those of the other structurally analogous clusters, in which the loosely coordinated ligand is trans to μ₂-S atom A summary of Mo-Mo, Mo-L bonding for such clusters is given.更多还原