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研究生: 劉世鈞
Liu, Shih-Jiung
論文名稱: 2,2-聯咪唑二價銅錯合物之立體化學,光譜及鍵結性質研究
Stereochemistry, Spectroscopic and Bonding Properties of 2,2-
指導教授: 蘇展政
Su, Chan-Cheng
學位類別: 博士
Doctor
系所名稱: 化學系
Department of Chemistry
論文出版年: 1995
畢業學年度: 83
語文別: 中文
論文頁數: 156
中文關鍵詞: 鍵結性質2,2-聯咪唑立體化學光譜高斯交疊解析偏極光光譜
英文關鍵詞: bonding properties, 2,2-biimidazole, stereochemistry, spectroscopic
論文種類: 學術論文
相關次數: 點閱:397下載:5
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  • 本研究係以 2,2'-聯咪唑為主要研究的配子, 共合成四個系列二價銅
    錯合物:
    (1) [Cu(dien)(LL)]X2系列, 其中 dien 為二乙基三胺, LL 有乙二胺
    (en), 1,10-二氮雜菲(phen), 2,2'-聯毗啶(bpy), 2,2'-聯咪唑(bimH2), X
    為 ClO4-或 CF3SO3-.
    (2) Cu(LL)2X2系列, 其中 LL有乙二胺 (en), 1,10-二氮雜菲(phen),
    2,2'-聯毗啶(bpy), 2,2'-聯咪唑 (bimH2), X為 ClO4-或 CF3SO3-.
    (3) Cu(bimH2)( LL)(ClO4)2系列, 其中 LL 有乙二胺(en), 1,10-二氮
    雜菲(phen), 2,2'-聯毗啶(bpy), 和N,N'- 二甲基乙二胺(dmen).
    (4) Cu(ImH)4X2 系列, X 有 CF3SO3-, NO3-, ClO4-, SO42- 和
    Cu(bimH2)(L)2(ClO4)2 系列, L 有咪唑(ImH), 4-甲基咪唑(4MImH),
    N-甲基咪唑(NMIm).
    利用元素分析及紅外光譜來確定錯合物的合成. 紫外-可見光光譜,
    電子順磁共振光譜和 X -光單晶繞射結構解析等方法, 研究各個錯
    合物分子構造, 軌域能層分佈及鍵結性質. 每一系列均有一個供參
    考比較的 X -光單晶繞射結構解析, 其資料如下:
    (1) [Cu(dien)(bimH2)](ClO4)2, 單斜晶系, 空間群 P21/c, 晶格常數 a
    = 11.001(2) , b = 12.412(3) , c = 14.456(2) , β = 94.28(1). 晶
    胞值為 4 , 精算值 R = 0.071, Rw = 0.085.
    (2) [Cu(bimH2)(bpy)(ClO4)](ClO4).H2O, 三斜晶系, 空間群 P1, 晶格
    常數 a = 7.206(4) , b = 12.269(2) , c = 12.682(3) , α = 106.68(2)
    , β = 96.91(3), γ = 93.94(3). 晶胞值為 2 , 精算值 R = 0.051, Rw
    = 0.057.
    (3) [Cu(bpy)2(CF3SO3)2], 三斜晶系, 空間群 P1, 晶格常數 a =
    8.595(1) , b = 8.591(1) , c = 18.830(5) , α = 95.84(2), β =
    95.87(2), γ = 108.65(1). 晶胞值為 2 , 精算值 R = 0.036, Rw =
    0.043.
    (4) [Cu(HIm)4(CF3SO3)2], 三斜晶系, 空間群 P21/n, 晶格常數 a =
    9.116(4) , b = 9.559(1) , c = 14.664(5) , β = 106.19(3). 晶胞值
    為 2 個分子, 精算值 R = 0.041, Rw = 0.052.
    將每系列錯合物的紫外-可見光光譜均作高斯交疊解析, 可觀測本
    研究主配子 2,2'-聯咪唑 (bimH2) 在錯合物的立體空間位置及影響
    鍵結軌域之變化情況, 並培養出
    [Cu(bimH2)(bpy)(ClO4)](ClO4).(H2O) 和 Cu(bpy)2(CF3SO3)2 薄片
    單晶, 測其偏極光光譜及作高斯交疊解析, 發現配子的 π 電子和銅
    原子的 d 軌域有不同程度的交互作用. d 軌域能層則依分子內原子
    對稱性, 及空間位置而有分裂或升降現象, 主配子在錯合物的立體
    空間位置明顯地和配子的π參與性能有關. 比較各系列銅混合配
    子錯合物發現主配子在五配位的 CuN5 系統中具有 π 接受 性質
    (π-accepting property); 在四配位的 CuN4 系統, 混合配子銅錯合物
    為 Cu(bimH2)(L)2(ClO4)2 ,主配子 2,2'- 聯咪唑的 π 電子則有 π
    供給性質 (π-donating property) .

    Four kinds of mixed ligand biimidazole copper(II) complexes have been
    prepared. These are :
    (1) [Cu(dien)(LL)]X2 type, where dien stands for diethylenetriamine
    (dien), and LL for ethylenediamine (en), 1,10-phenanthroline (phen),
    2,2'-bipyridine (bpy), 2,2'-biimidazole (bimH2) and X for ClO4- or
    CF3SO3-.
    (2) Cu(LL)2X2 type, where LL stands for ethylenediamine (en), 1,10-
    phenanthroline (phen), 2,2'-bipyridine (bpy), 2,2'-biimidazole (bimH2)
    and X for ClO4- or CF3SO3-.
    (3) Cu(bimH2)(LL)(ClO4)2 type, where LL stands for1,10-
    phenanthroline (phen), 2,2'-bipyridine (bpy), N,N-
    dimethylenethylenediamine (dmen) and ethylenediamine (en).
    (4) Cu(ImH)4X2 and Cu(bimH2)(L)2(ClO4)2 type, where X is
    CF3SO3-, NO3-, ClO4- and SO42- and L includes imidazole (ImH), 4-
    methylimidazole (4MImH) and N-methylimidazole (NMIm).
    The mixed ligand biimidazole copper(II) complexes have been
    characterized by elemental analyses, and electronic, vibrational, and
    spectroscopic measurements. X-ray crystal structures of the following
    complexes have been determined from three-dimensional X-ray
    diffraction data.
    (1) [Cu(dien)(bimH2)](ClO4)2, monoclinic, space group P21/c, a =
    11.001(2) , b = 12.412(3) , c = 14.456(2) , β = 94.28(1). z = 4,
    R = 0.071, Rw = 0.085.
    (2) [Cu(bimH2)(bpy)(ClO4)](ClO4).H2O, triclinic, space group P1, a
    = 7.206(4) , b = 12.269(2) , c = 12.682(3) , α = 106.68(2), β =
    96.91(3), γ = 93.94(3). z = 2, R = 0.051, Rw = 0.057.
    (3) [Cu(bpy)2(CF3SO3)2], triclinic, space group P1, a = 8.595(1) , b
    = 8.591(1) , c = 18.830(5) , α = 95.84(2), β = 95.87(2), γ =
    108.65(1). . z = 2, R = 0.051, Rw = 0.057.. z = 2, R = 0.036, Rw =
    0.043.
    (4) [Cu(ImH)4(CF3SO3)2], monoclinic, space group P21/n, a =
    9.116(4) , b = 9.559(1) , c = 14.664(5) , β = 106.19(3). z = 2,
    R = 0.041, Rw = 0.052.
    The sequence of the d orbitals has been deduced from Gaussian analysis
    of the LF spectra. Single crystal polarized spectra for
    [Cu(bimH2)(bpy)(ClO4)](ClO4)(H2O) and Cu(bpy)2(CF3SO3)2 have
    been performed and analyzed. Bonding properties of biimidazole in
    copper(II) complexes are elucidated and vary considerablly depending
    on the structures of the complexes. In [Cu(dien)(bimH2)](ClO4)2
    square bipyramidal system, biimidazole ligand is perpendicular to the
    CuN4 basal plane showing strong π-accepting character. In
    Cu(bimH2)2(ClO4)2 elongated Ohl system, biimidazole ligand is
    bonded in the basal plane, and no π involved. In the
    Cu(bimH2)(L)2(ClO4)2 system, biimidazole ligand is bonded in the
    basal plane exhibits π donating properties.
    Four kinds of mixed ligand biimidazole copper(II) complexes have been

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