物理化学学报 >> 1988, Vol. 4 >> Issue (06): 611-616.doi: 10.3866/PKU.WHXB19880609

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簇合物配基置换反应的研究——Mo3S4(μ-dtp)(η2-dtp)2(η1-dtp)(bpy)的合成与晶体结构

黄明东; 卢绍芳; 黄建全; 黄金陵   

  1. 中国科学院福建物质结构研究所, 福州大学
  • 收稿日期:1987-02-23 修回日期:1987-12-05 发布日期:1988-12-15
  • 通讯作者: 黄明东

RESEARCH ON SUBSTITUTION REACTION OF LIGANDS IN Mo3S4(dtp)4(H2O)——SYNTHESIS AND CRYSTAL OF Mo3S4(μ-dtp)(η2-dtp)2(η1-dtp)(bpy)

Huang Mingdong*; Lu Shaofang; Huang Jianquan; Huang Jinling   

  1. Fujian Institute of Resaerch on the Structure of Matter; Academia Sinica; and Fuzhou University
  • Received:1987-02-23 Revised:1987-12-05 Published:1988-12-15
  • Contact: Huang Mingdong

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摘要： 应用X-射线单晶衍射方法, 测定2,2-联吡啶(bpy)和簇合物MO_3S_4(μ-dtp)(dtp)_3(H_2O)(Ⅰ)反应产物褰峁埂ａ果? 产物为Mo_3S_4(μ-dtp)(η~2-dtp)_2(η~1-dtp)(bpy)(Ⅱ), 即联吡啶置换了簇合物(Ⅰ)中的端基(H_2O)和端基(dtp)中的一啮。簇合物(Ⅱ)晶体属三斜晶系。晶胞参数为:a=1.3638(3); b=1.3983(3); c=1.4699(2) nm, a=95.57(2)°, β=91.87(2)°, γ=117.40(2)°; V=2.4676 nm; Z=2; D_C=1.767 g·cm~(-3)。晶体的空间群为P1。最终偏离因子R=0.069, R_w=0.076。本文结合过去对簇合物(Ⅰ)进行的四种不同类型的置换反应的研究, 进行了必要的讨论。并指出本文中的反应是松散本位促进的配基置换反应。

Abstract: From the reaction of Mo_2S_4(μ-dtp)(dtp)_3(H_2O) (I) (dtp = diethyldithiophosphanato) with 2,2'-bipyridine, the product Mo_3S_4(μ-dtp)(η~2-dtp)_2(η~1-dtp)(bpy)(Ⅱ) has been isolated, and characterized by X-ray crystallography. Crystal: (Ⅱ) belongs to triclinic system in space group Pi with crystallographic parameters as following., a=1.3638(3), b=1.3983(3), c=1.4699(2) nm, α=95.57°, β=91.87°, γ=117.40°; V=2.467(2) nm, Z=2, Dc=1.767 g.cm~(-3), final R=0.069, R_w= 0.076. The results of the structure determination show that the coordinated H_2O ligand and one of sulphur atoms of dtp on the Mo(3) atom of cluser(Ⅰ) have been substituted by 2,2′-bipyridine ligand. It has been pointed out that the ligand substitution reaction reported here is closely correlated with the existence of loosely-coordinated site in cluster (Ⅰ). In addition, the other types of substitution reactions of ligands are also discussed.