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本文报道了具有局部松散配位的三核钼原子簇{Mo_3(μ_3-S)(μ-S)_3[S_2P(OEt)_2]_4·P(C_6H_5)_3}·(0.86CH_2Cl_2)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=2950A~3,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。
In this paper, we report the synthesis and distribution of three-nuclear molybdenum clusters {Mo_3 (μ_3-S) (μ-S) _3 [S_2P (OEt) _2] _4 · P (C_6H_5) _3} · (0.86CH_2Cl_2) with loosely- Crystal structure. The crystal belongs to the triclinic system, the space group is PI, the unit cell parameters a = 10.472 (4), b = 14.375 (2), c = 21.695 (3) A; , γ = 72.22 (2) °, V = 2950A ~ 3, D_c = 1.693g · cm ~ (-3) and Z = 2. On the CAD-4 four-circle diffractometer, ) Of 4840 diffraction points. The structure was solved by heavy atom method and differential electron density method, and corrected by full matrix least square method. The final deviation factor was 0.058. The Mo-Mo bonds of cluster molecules are 2.731 (1), 2.748 (1), 2.753 (1) A. The coordination length of the P atom of Mo atom and triphenylphosphine is Mo-P2.647 (3) A, Longer than normal Mo-P covalent single bond. The triphenylphosphine group is in the para position of the triple bridge S atom in the coordination polyhedron of Mo and exhibits a different ligand coordination position from the other ligands of this class. This paper summarizes the bond formation of Mo-Mo and Mo-L of such clusters.