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化学学报 ›› 2004, Vol. 62 ›› Issue (17): 1626-1634. 上一篇    下一篇

研究论文

N,N-二苄基二硫代氨基甲酸金属配合物的合成、晶体结构及其热稳定性研究

范军1, 殷霞1, 章伟光1, 张启交1, Lai Chian-Sing2, Tiekink Edward R. T.2, 范毅3, 黄庙由3   

  1. 1. 华南师范大学化学系, 广州, 510631;
    2. 新加坡国立大学化学系, 新加坡, 117543;
    3. 华南理工大学高分子材料科学与工程系, 广州, 510641
  • 投稿日期:2004-01-12 修回日期:2004-03-23 发布日期:2014-02-17
  • 通讯作者: wgzhang@scnu.edu.cn
  • 作者简介:章伟光E-mail:wgzhang@scnu.edu.cn
  • 基金资助:
    广东省自然科学基金(No.990463),广东省教育厅自然科学基金(No.1999-89)和新加坡国立大学(No.R-143-000-213-112)资助项目.

Synthesis,Structure and Thermal Stability of Metal Complexes with N, N-Dibenzyl Dithiocarbamate

FAN Jun1, YIN Xia1, ZHANG Wei-Guang1, ZHANG Qi-Jiao1, LAI Chian-Sing2, TIEKINK E. R. T.2, FAN Yi3, HUANG Miao-You3   

  1. 1. Department of Chemistry, South China Normal University, Guangzhou 510631, China;
    2. Department of Chemistry, National University of Singapore, Singapore 117543, Singapore;
    3. Department of Polymer Material and Science, South China University of Technology, Guangzhou 510641, China
  • Received:2004-01-12 Revised:2004-03-23 Published:2014-02-17

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报道了四种二苄基二硫代氨基甲酸金属配合物[Cd(DBTC)2]2(1),[Hg(DBTC)2](2),[Nd(DBTC)3·2H2O]和[Nd-(DBTC)3(HMPA)2](3)(DBTC=N,N-二苄基二硫代氨基甲酸;HMPA=六次甲基磷酰胺)的合成及其红外光谱.配合物1～3的晶体结构用X射线晶体衍射分析确定.配合物1,C30H28N2CdS4,Mr=657.18,单斜晶系,空间群P21/n,α=1.11098(4)nm,b=1.56325(5)nm,c=1.66695(5)nm,β=97.9220(10)埃琙=4,R=0.044,wR1=0.091.2,C30H28N2HgS4,Mr=745.37,正交晶系,空间群Pbcn,α=1.64738(1)nm,b=1.86418(14)nm,c=0.94000(6)nm,Z=4,R=0.0387,wR1=0.0965.3,C57H78N9NdO2P2S6,Mr=1319.82,单斜晶系,空间群P21/c,α=1.30389(9)nm,b=3.4708(3)nm,c=3.1210(2)nm,β=96.527(2)埃琙=8,R=0.1023,wR1=0.2203.1为二聚体,中心离子的配位结构为扭曲的四方锥;2和3均为单核配合物,但中心离子的配位结构不同,2为扭曲的四面体,而3则为变形的十二面体.配合物的热重分析结果表明配合物1,2在加热失重的过程中可能伴随有升华现象,有望作为MOCVD的前驱物.

关键词: 二硫代氨基甲酸, 配合物, 晶体结构, 合成, 热稳定性

Four metal complexes, which were shown as [Cd(DBTC)2]2 (1), [Hg(DBTC)2] (2), [Nd(DBTC)3·2H2O] and [Nd(DBTC)3(HMPA)2] (3) (where DBTC=N,N-dibenzyl dithiocarbamate, HMPA=hexamethylphosphoramide), were synthesized and characterized by IR spectra.The structures of complexes 1～3 were determined by X-ray crystallography analysis.Crystal data of compound 1: C30H28N2CdS4, Mr=657.18, monoclinic, space group P2 1/n, a=1.11098(4) nm, b=1.56325(5) nm, c=1.66695(5) nm, β=97.9220(10)°, Z=4, R=0.044, wR1=0.091.Crystal data of compound 2: C20H28N2HgS4, Mr=745.37, orthorhombic, space group Pbcn, a=1.64738(1) nm, b=1.86418(14) nm, c=0.94000(6) nm, Z=4, R=0.0387, wR1=0.0965.Crystal data of compound 3: C57H78N9NdO2P2S6, Mr=1319.82, monoclinic, space group P2 1/c, a=1.30389(9) nm, b=3 4708(3) nm, c=3.1210(2) nm, β=96.527(2)°, Z=8, R=0.1023, WR1=0.2203.Compound 1 is a dimer, and the Cd(Ⅱ) ion has an approximate tetragonal pyramidal geometry.Compounds 2 and 3 are monomers and show different coordination polyhedron.The Hg(Ⅱ) ion has a distorted tetrahedral coordination polyhedron, while the Nd(Ⅲ) ion exhibits distorted dodecahedral geometry.Thermal gravity (TG) data indicate that compounds 1 and 2 may be sublimed and decomposed in the course of heating and they might be expected to be useful precursors for MOCVD.

Key words: dithiocarbamate, complex, crystal structure, synthesis, thermal stability