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研究生: 戴彩雲
TAI TSAI YUN
論文名稱: 血青素模型錯合物的研究:N,N-雙(苯咪唑-2-甲基)胺之二價銅混合配子錯合物的合成、結構及鍵結性質研究
指導教授: 蘇展政
Su, Chan-Cheng
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
畢業學年度: 87
語文別: 中文
中文關鍵詞: 血青素模型錯合物高斯交疊解析
英文關鍵詞: hemocyanine
論文種類: 學術論文
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  • 本研究以雙(甲基啶)胺(dipica)及N,N-雙(1-甲基苯咪-2-甲基)甲基胺(CH3bimmaCH3)為主要配子,合成了下列錯合物:[Cu(dipica)(acac)](ClO4)(1)、[Cu(CH3bimmaCH3)(acac)](Et3NH)-(H2O)(ClO4)2(2)、[Cu(CH3bimmaCH3)(CH3CN)](ClO4)2(3)及[Cu(CH3bimmaCH3)(phen)](ClO4)2(4),其中acac為2,4-戊二酮、phen為1,10-二氮雜菲。利用元素分析、紅外光光譜、紫外光-可見光吸收光譜,電子順磁共振光譜及X-光單晶結構解析等方法,完成錯合物的結構鑑定及鍵結性質之探討。
    目前已有X-光單晶結構解析的錯合物有:
    1. [Cu(dipica)(acac)](ClO4)(1)
    屬於三斜晶系(triclinic),空間群為PT,晶格常數a = 7.2374(2) A, b = 11.3015(2) A, c = 13.5843(2) A,  = 65.702(1)°,  = 79.625(1)°,  = 82.243(1)°, 每單位晶格內含有2個分子(Z = 2),精算值R = 0.0376, Rw = 0.0377。
    2. [Cu(CH3bimmaCH3)(acac)](Et3NH)(H2O)(ClO4)2(2)
    屬於三斜晶系(triclinic),空間群為PT,晶格常數a = 12.1122(12) A, b = 12.9011(12) A, c = 14.7641(14) A,  = 64.476(2)°,  = 67.479(2)°,  = 75.567(2)°,每單位晶格內含有2個分子(Z = 2),精算值R = 0.0813, Rw = 0.2084。
    3. [Cu(CH3bimmaCH3)(CH3CN)](ClO4)2(3)
    屬於單斜晶系(monoclinic),空間群為P21/c,晶格常數a = 11.243(3) A, b = 12.1801(21) A, c = 19.099(3) A,  = 104.119(22)°, 每單位晶格內含有4個分子(Z = 4),精算值R = 0.057, Rw = 0.053。
    由可見光光譜的高斯交疊解析結果,本研究錯合物的d軌域排列順序,依結構不同,可分為下列三種:
    (a) 錯合物(1)和(2):
    dxy >> dz2 > dx2-y2 > dyz > dxz
    (b) 錯合物(3):
    dx2-y2 >> dxy > dxz , dyz > dz2
    (c) 錯合物(4):
    dx2-y2 >> dz2 > dxy > dxz , dyz
    綜合本研究的結果得知,在錯合物(1)和(2)中,dipica和CH3bimmaCH3為facial的鍵結模式,推測是acac為-donor性質的配子所造成。因此,配子的鍵結模式與錯合物中其他配子的性質有極大的關聯。

    Four mixed ligand copper (II) complexes, [Cu(dipica)(acac)](ClO4)(1), [Cu(CH3bimmaCH3)(acac)](Et3NH)(H2O)(ClO4)2(2), [Cu(CH3bimmaCH3)(CH3CN)](ClO4)2(3) and [Cu(CH3bimmaCH3)(phen)]-(ClO4)2(4), where dipica = dipicolylamine, CH3bimmaCH3 = N,N-bis(1-methylbenzimidazol-2-ylmethyl)methylamine, acac = acetylacetonate, phen = 1,10-phenanthroline, have been synthesized and characterized by elemental analyses, infrared, electronic, and epr spectroscopic measurements.
    By single-crystal X-ray diffraction method, the crystal and molecular structures of [Cu(dipica)(acac)](ClO4)(1), [Cu(CH3bimmaCH3)(acac)]-(Et3NH)(H2O)(ClO4)2(2) and [Cu(CH3bimmaCH3)(CH3CN)](ClO4)2(3) have been determined. The crystal data of these complexes are described below:
    (a) [Cu(dipica)(acac)](ClO4)(1) crystallizes in the triclinic, space group PT with a = 7.2374(2) A, b = 11.3015(2) A, c = 13.5843(2) A,  = 65.702(1)°,  = 79.625(1)°,  = 82.243(1)°, Z = 2, R = 0.0376 and Rw = 0.0377.
    (b) [Cu(CH3bimmaCH3)(acac)](Et3NH)(H2O)(ClO4)2(2) crystallizes in the triclinic, space group PT with a = 12.1122(12) A, b = 12.9011(12) A, c = 14.7641(14) A,  = 64.476(2)°,  = 67.479(2)°,  = 75.567(2)°, Z = 2, R = 0.0813 and Rw = 0.2084.
    (c) [Cu(CH3bimmaCH3)(CH3CN)](ClO4)2 (3) crystallizes in the monoclinic, space group P21/c with a = 11.243(3) A, b = 12.1801(21) A, c = 19.099(3) A,  = 104.119(22)°, Z = 4, R = 0.057 and Rw = 0.053.
    The solution LF spectra of these complexes were deconvoluted into Gaussian component bands. The results were employed to interpret the electronic and bonding properties of the copper (II) complexes. The sequences of d orbitals were assigned as following:
    (a) (1) and (2):
    dxy >> dz2 > dx2-y2 > dyz > dxz
    (b) (3):
    dx2-y2 >> dxy > dxz , dyz > dz2
    (c) (4):
    dx2-y2 >> dz2 > dxy > dxz , dyz
    In conclusion, the tridentate ligands, dipica and CH3bimmaCH3, tend to bind to copper (II) with a facial configuration when the other binding ligand is acac. The configurations of the tridentate ligands are dependent on the coordination capabilities of other ligands presented in the complexes.

    中文摘要 Ⅰ 英文摘要 Ⅲ 第一章 緒論 第一節 研究動機與目的 1 第二節 背景 3 第二章 實驗部分 第一節 實驗儀器及藥品 20 第二節 一價銅與氧的反應實驗 23 第三節 配子及錯合物的合成 26 第三章 結果與討論 第一節 一價銅與氧的反應探討 31 第二節 配子及錯合物的合成探討 34 第三節 X-光結構解析 36 第四節 紅外光光譜 46 第五節 電子順磁共振光譜 48 第六節 電子吸收光譜 55 第七節 可見光光譜的高斯交疊解析 59 第四章 結論 73 參考文獻 75

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