【摘要】 合成了具有一定空阻的配体α-萘硫酚及其铜的配合物[α-C₁₀H₇SCu]_n.它在PPh₃存在下与CS₂反应,获得了CS₂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[（Ph₃P）₂Cu(α-C₁₀H₇SCS₂)]·CS₂（1）.由此单核插入产物与混合溶剂CH₂Cl₂/CH₃OH反应,培养出产物的晶体,测定结构为（Ph₃P）₂Cu(α-C₁₀H₇S)₂Cu（PPh₃）（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流代黄原酸α-C₁₀H₇SCS₂^-的两个S原子和两个Ph₃P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PPh₃的磷原子配位,而Cu（2）则与2个桥连的硫原子和2个PPh₃的磷原子形成变形四面体配位.更多还原

【Abstract】 With sterically hindered 1 - naphthalenethiol ligand, the copper complex [α- C10H7SCu]n reacted with CS2, in the presence of Ph3P, to give a product of CS2 insertion into Cu-S bonds. The crystal structure of the product is [ (Ph3P)2Cu(α - C10H7SCS2 ) ] ·CS2 (1) , determined by the X - ray diffraction method. The mononuclear insertion product (1) reacted with mixed solvents CH2Cl2 /CH3 OH to form orange crystals, the structure of which is (Ph3P)Cu(α - C10H7S)2Cu ( PPh3 )2 (2). In the complex (1), the Cu atom is pseudotetrahedrally coordinated by two S atoms of the thioxanthate ligand (α - C10H7SCS2-) and two P atoms of Ph3 P. 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 Ph3P; while Cu(2) is coordinated by two bridge S atoms and two P atoms of Ph3P 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)nm3, Dc = 1.371g/cm3, 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)nm3, Dc = 1.320g/cm3, Z = 4, R = 0.0794 for 5673 independent reflections.更多还原