化学学报 ›› 2000, Vol. 58 ›› Issue (7): 866-870. 上一篇    下一篇

研究论文

[Ph~3P)~2Cu(α-C~1~0H~7SCS~2)]·CS~2和 (Ph~3P)~2Cu(α-C~1~0H~7S)~2Cu (PPh~3)的合成与晶体结构

汤卡罗;金祥林;卢羽;龙耀玲;崔澎;唐有祺   

  1. 北京大学物理化学研究所.北京(100871)
  • 发布日期:2000-07-15

Synthesis and crystal structures of 5[Ph~3P)~2Cu(α-C~1~0H~7SCS~2)]· CS~2 and (Ph~3P)~2Cu(α-C~1~0H~7S)~2Cu(PPh~3)

Tang Kaluo;Jin Xianglin;Lu Yu;Long Yaoling;Cui Peng;Tang Youqi   

  1. Beijing Univ, Inst Phys Chem.Beijing(100871)
  • Published:2000-07-15

合成了具有一定空阻的配体α-萘硫酚及其铜的配合物[α-C~1~0H~7SCu]~n。它在PPh~3存在下与CS~2反应,获得了CS~2在其Cu-S键中的插入产物,用X射线衍射法测得其晶体结构为[Ph~3P)~2Cu(α-C~1~0H~7SCS~2)]·CS~2(1)。由此单核插入产物与混合溶剂CH~2Cl~2/CH~3OH反应,培养出产物的晶体,测定结构为(Ph~3P)~2Cu(α-C~1~0H~7S)~2Cu(PPh~3)(2)。化合物(1)是以铜原子为中心的配合物,铜原子以变形四面体与硫代黄原酸α-C~1~0H~7SCS~2^-的两个S原子和两个Ph~3的P原子配位。化合物(2)为中性双核铜配合物,2个萘硫酚配体的硫原子桥连2个铜原子,组成了四边形。2个铜原子配位情况不同,Cu(1)采用平面三配位构型,分别与2个桥连的硫原子和1个PPh~3的磷原子配位,而Cu(2)则与2个桥连的硫原子和2个PPh~3的磷原子形成变形四面体配位。

关键词: 三苯基膦, 萘P, 硫酚, 铜络合物, 二硫化碳, X射线衍射分析, 晶体结构, 插入反应

With sterically hindered 1-naphthalenethiol ligand, the copper complex [α-C~1~0H~7SCu]~n reacted with CS~2, in the presence of Ph~3P, to give a product of CS~2 insertion into Cu-S bonds. The crystal structure of the product is [Ph~3P)~2Cu(α-C~1~0H~7SCS~2)]· CS~2(1), determined by the X-ray diffraction method. The mononuclear insertion product (1) reacted with mixed solvents CH~2Cl~2/CH~3OH to form orange crystals, the structure of which is (Ph~3P)~2Cu(α- C~1~0H~7S)~2Cu(PPh~3)(2). In the complex (1), the Cu atom is pseudotetrahedrally coordinated by two S atoms of the thioxanthate ligand (α-C~1~0H~7SCS~2^-) and two P atoms of Ph~3P. Compound (2) is a neutral dinuclear copper complex, in which the two S atoms of the 1- naphthalenethiol ligands bridge two Cu atoms to form a quadrilateral. The two Cu atoms have different coordination situation. Cu(1) is planar trigonally coordinated by two bridge S atoms and one P atom of Ph~3P; while Cu(2) is coordinated by two bridge S atoms and two P atoms of Ph~3P to form a distorted tetrahedron. Crystal data for complex (1): space group p-1, a=1.4200(3) nm, b=1.5072(3) nm, c=1. 1747(2) nm, α=108.09(3), β=112.73(3), γ=75.41(3)°, V=2.1791(7) nm^3, D~c=1.371 g·cm^3, Z=2, R=0.0430 for 7660 independent reflections. Crystal data for complex(2) : space group C2, a=2.0771(4) nm, b=1.6340(3) nm, c=1.8861(4) nm, β=104.40(3)°, V=6.200(2) nm^3, D~c=1.320 g·cm^3, Z=4, R=0.0794 for 5673 independent reflections.

Key words: TRIPHENYLPHOSPHINE, NAPHTHALENE P, THIOPHENOLS, COPPER COMPLEX, CARBON DISULFIDE, X-RAY DIFFRACTION ANALYSIS, CRYSTAL STRUCTURE, INSERTION REACTION

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