【作者】 虞虹；

【导师】 纪顺俊；

【作者基本信息】 苏州大学 ， 有机化学， 2004， 硕士

【摘要】 近二十多年来，具有含氮配体的金属有机化合物合成与结构表征是金属有机化学中一个引人注目的研究领域。这些化合物的结构化学丰富多彩，并且在工业催化，生命科学以及材料科学中均有着十分重要的应用前景。 本论文一是通过[PPh₄][Cp^*WS₃]与CuI，CuBr，dppm在乙腈中反应；二是通过已知的金属有机簇合物[（Cp^*WS₃）₃Cu₇（CH₃CN）₉]（PF₆）₄和过量吡啶反应；三是通过乙二胺或2，5-二（4’-吡啶基）-1，3，4-三唑(C₁₂H₉N₅)直接与金属盐反应，得到了六个新金属有机化合物。它们分别是：[PPh₄][Cp^*WS₃（CuI）₂（CuBr）（dppm）]（1），[Cp^*WS₃Cu₃（Py）₆]（PF₆）₂·PY （2）和[Pb（en）₂Cl₂] （3），[Ni(C₁₂H₉N₅)₂（H₂O）₂]（NCS）₂ （4），[M(C₁₂H₉N₅)₂（H₂O）₂]（L）₂·4H₂O（5：M=Co；L=Cl；6：M=Cu；L=NO₃）。化合物1-6分别用元素分析，红外光谱等进行了表征。其中1-3用CCD X-射线单晶衍射仪测定了晶体结构。簇合物1的簇阴离子是由2个CuI基团，一个CuBr基团，一个[Cp^*WS₃]^-单元通过三个μ₃-S桥联而成的不完整立方烷型结构，其中2个CuI基团再由dppm桥联起来；簇合物2的二价簇阳离子[Cp^*WS_sCu₃（Py）₆]²⁺具有一个网兜状WS₃Cu₃簇核结构，其中每个铜原子均与二个μ₃-S及二个吡啶分子配位；化合物3中，Pb原子呈八面体几何构型，双齿配体乙二胺以N原子与邻近的Pb原子相连，形成一维链状聚合结构。 簇合物1—6的合成及表征不仅为含氮配体的金属有机化合物家族增添了新的成员，同时也为此类化合物的物理和化学性质如光限制性、荧光性质的研究打下了基础。更多还原

【Abstract】 In the past twenty years, synthesis and structural characterization of organometallic compounds containing N-donor ligands remains a hot topic in organometallic chemistry. This is due to their rich structural diversity, their potential applications in industrial catalytic systems, biochemical systems, and material science.This thesis reports isolation of six novel oganometallic compounds containing N-donor ligands through reactions of [PPh4][Cp*WS3] with Cul, CuBr and dppm, or reactions of [(Cp*WS3)Cu7(CH3CN)9](PF6)4 with excess Py, or reactions of M(II) (M = Pb, Ni, Co, Cu) with en or Ci2H9N5. They are [PPh4][Cp*WS3(CuI)2(CuBr)(dppm)] (1) , [Cp*WS3Cu3(Py)6](PF6)2’Py (2), [Pb(en)2Cl2] (3), [Ni(C12H9N5)2(H2O)2](NCS)2 (4), [M(C12H9N5)2(H2O)2](L)2-4H20 (5: M = Co; L = Cl; 6: M = Cu; L = NO3). Compounds 1-6 were characterized by elemental analysis, and IR spectra, and the crystal structure of 1-3 were determined by X-ray crystallography. The anion structure of 1 contains an incomplete [WS3Cu3] cubane core in which one CuBr and two CuI units are coordinated by one [Cp*WS3]~ moiety via three n3-S atoms. The [Cp*WS3Cu(Py)6]+ cation of 2 has a nido-like [WS3Cu3] structure in which each Cu is coordinated by two 3-S and two Py molecules. In the structure of 3, the lead atom displays a distorted octahedral coordination geometry. The bidentate ethylenediamine (en) ligands further interconnect the neighboring Pub atoms to form one-dimensional chain array.The synthesis and structural characterization of 1-6 not only rich the structural chemistry of oraganometallic compounds, but also lay foundation for the studies of their physical and chemical properties such as optical limiting performance, luminescence, etc..更多还原