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化学学报
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化学学报 ›› 1993, Vol. 51 ›› Issue (1): 52-58. 上一篇    下一篇

研究论文

CS2在Cu-S键中的插入反应的研究3:[Cu(S2CSC6H2Bu3^t-2,4,6]4.4C2H5OH的合成与晶体结构

汤卡罗;吴德冬;金祥林;唐有祺   

  1. 北京大学物理化学研究所
  • 发布日期:1993-01-15

Insertion reaction of CS2 into Cu-S bonds Pt.3: Preparation and crystal structure of [Cu(S2CSC6H2Bu3^t-2,4,6)]44C2H5OH

TANG KALUO;WU DEDONG;JIN XIANGLIN;TANG YOUQI   

  • Published:1993-01-15

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2,4,6-三特丁基硫酚铜[Cu(SC6H2Bu3^t-2,4,6-)]n与CS2的反应产物, 用CS2-乙醇重结晶得黄色晶体, 经X射线单晶衍射法测定, 其结构为[Cu(S2CSC6H2Bu3^t-2,4,6-)].晶体属四方晶系, 空间群142d.a=b=1.7079(3)nm,c=3.5228(10)nm, V=10.275(6)nm3, Dc=1.19gcm^-3, Z=4.1863个衍射点参与修正,R=0.0559.四个铜原子形成变形四面体, CS2在全部四个Cu-S键中插入, 形成硫代黄原酸配体(RSCS2^-).配体中两个硫原子参与配位, 其中一个S桥连两个Cu原子, 另一个S端位于第三个Cu原子。每个Cu原子都采取平面三配位方式。CS2插入形成的CS2基团基本平面, C-S平均键长为0.1712nm。本文还对CS2, 在Cu-S和Ag-S键中插入反应产物的结构特点及影响反应的因素进行了讨论。

关键词: 晶体结构测定, 影响因素, 硫酸, 二硫化碳, 黄原酸类, 化学键, 铜化合物, 插入反应, 特丁基, 配位化学

Colorless comples [CuSC6H2Bu3^t-2,4,6]n reacted with CS2 to give a yellow product, which was recrysterized from CS2-C2H5OH to form yellow crystals, the structure of the crystal was shown to be [Cu(S2CSC6H2Bu3^t-2,4,6)]4.4C2H5OH by single srystal X-ray diffraction method. the crystal belongs to the tetraponalspace group 142d with unit cell parameters: a=b=1.7079(3)nm , c=3.5228(10)nm, V=10.275(6)nm^3, Dc=1.198g cm^-3, Z=4. the structure was refined to R=0.0559 for 1863 reflections. in the molecule , cCu4 cluster has a distorted tetrahedral configuration. surrounding this tetrahedron are four thioxnthate lignds (RSCS2) formed by insertion fo CS2 into Cu-S bonds the ligand coordinates to copper atoms through two sulfur atoms, one of which baidges two pper atoms, while the other coordinates tothe third copper atom. the coordination geometry of eacch copper atom is planar trigonal. the trithiocarbonato CS3 group resulted from insertion of CS2 into Cu-S bond is approximately coplanar the mean C-S bond length of CS3 is 0.1712 nm. the structural charaoteeristeic and the faotors influencing the insertion reaction are disoussed in the paper.

Key words: CRYSTAL STRUCTURE DETERMINATION, INFLUENCING FACTORS, SULFURIC ACID, CARBON DISULFIDE, XANTHOGENIC ACIDS, CHEMICAL BONDS, COPPER COMPOUNDS, INSERTION REACTION, TERT.-BUTYL GROUP, COORDINATE CHEMISTRY

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