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研究生： 陳健安
Chen Chien-An
論文名稱： 二價鎳大環四胺基錯合物之配位化學研究
Coordination Chemistry of Nickel(Ⅱ) Macrocyclic Tetraamine Complexes
指導教授： 鍾崇燊
Chung Chung-Sun
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2001
畢業學年度： 89
語文別： 中文
論文頁數： 145
中文關鍵詞： 大環 、四胺基
外文關鍵詞： Macrocyclic, Tetraamine
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    • 中文摘要
    本文所採用的四胺基十四元大環係直接利用有機合成方法以過氯酸乙二胺鹽類與α、β未飽和酮類進行邁可加成(Michael addition)再經縮合成環反應得到大環配位子，5,7,7,12,14,14－六甲基－1,4,8,11－四氮環十四元－4,1－1二烯及烷類配位子。這些配位子可與鎳(Ⅱ)離子反應，形成數種具有不對稱碳原子中心之立體化學異構物，並且已有部分異構物能夠有效地被分離出來或單離出來。

    這些金屬錯化合物的組態及構形異構物之差異性，已被利用化學方法及光譜分析方法上之證據加以區別與推測。本文利用IR光譜來研究各個異構物構形之差異對氮鎳鍵的IR光譜的影響來加以探討。

    此外當[α-Ni(rac-1,7-CTH)]2+與ethylenediamine(en)反應時會形成三元錯化合物，因此在25±0.1℃、離子強度0.1MNaClO4環境條件下，考慮ICB效應的影響，就單質子化物種而言速率決定步驟為第一個鍵的生成，而未質子化物種之速率決定步驟則發生在第二個鍵螯合成環時。

    最後，在所有形成反應中，配位子影響數率常數的改變可歸納出下列三個因素：一、立體效應，二、螯合成環大小，三、ICB的效應。

    The macrocyclic tetraamine ligands were synthesized by using of direct organic condensation reaction and then subjected to react with nickel(II) ion and followed by reduction to form C- diastereoisomeric complexes.
    These diastereoisomeric complexes were separated and ligand configuration and conformation were assigned on the basis of chemical and spectroscopical method. In order to investigate the effect of the structural variation of the nickel(II) macrocyclic tetraamine complexes upon Ni-N bonds has been examined with FTIR.

    The kinetics of ternary complex formation between [α-Ni(tet-b)](ClO4)2 and ethylenediamine were studied at 25±0.1℃ and μ=0.1 mol dm-3 (NaClO4) over a pH range of 7.38~8.37, covering an ethylenediamine concentration range of (2.00~10.00)×10-3 mol dm-3. The rate-determining step in the en path is ring closure whereas the Hen+ is the initial bond formation.

    The decelerating effects on the rate constant values of the complex formation path are due to : (1) steric hindrance; (2) the size of ring; (3)ICB effect.

    目 錄 目錄----------------------------------------------------------------------------------I 圖目錄-----------------------------------------------------------------------------Ⅲ 表目錄-----------------------------------------------------------------------------Ⅴ 中文摘要--------------------------------------------------------------------------Ⅸ 英文摘要--------------------------------------------------------------------------Ⅹ 第一章 緒論----------------------------------------------------------------------1 第二章 二價鎳與四胺基大環配位子之錯合物合成---------------------12 第三章 紅外線光譜法對 (5, 7, 7, 12, 14, 14－六甲基－1, 4, 8,12－四胺基十四員環)鎳(Ⅱ)錯化合物之不同異結構物之立體化學之探討---------------------------------------------------------------------21 一、 前言-------------------------------------------------------------------21 二、 實驗部分-------------------------------------------------------------29 三、 結果-------------------------------------------------------------------29 第四章 [α-Ni(tet-b)]2+三元錯合物之形成反應的動力學研究--------39 一、 前言-------------------------------------------------------------------39 二、 實驗部分-------------------------------------------------------------54 三、 結果-------------------------------------------------------------------56 四、 討論-------------------------------------------------------------------68 第五章 鎳(II)三元錯合物的晶體分析--------------------------------------77 一、 前言-------------------------------------------------------------------77 二、 二價鎳三元錯合物之合成----------------------------------------79 三、 討論-------------------------------------------------------------------79 第六章 結論---------------------------------------------------------------------84 參考資料--------------------------------------------------------------------------85 附錄--------------------------------------------------------------------------------93 化 學 教 材 與 教 法：軌域能階與電子組態--------------------119 讀書會：速率常數與平衡常數-----------------------------------------133 圖目錄 圖1-1 The structures of Heme, Chlorophyll and Vitamin B12.----------2 圖1-2 Synthesis of macrocyclic Ni(Ⅱ)-tetraamine complexes by using techniques of metal template.--------------------------------4 圖1-3 Geometrical isomers of the linear and macrocyclic tetraamine Ni(Ⅱ) complexes.----------------------------------------------------6 圖1-4 Configurational isomers of Ni(meso-1,7-CTH)2+(1-10)andNi(rac- 1,7-CTH)2+ (11-20).A plus sign at asymmetric centerindication that the hydrogen atom of center is above the planeof the macrocycle, and a minus sign, that is blow. Gaucheconformations of five-menbered chletate rings and chairconformations of six menbered chelate rings are indicated byheavier lines. The axial C5 and C12 methyl groups are indicated with an asterisk.-------------------------------------------7 圖 1–5 四胺基大環配位子與其鎳(Ⅱ)錯化合物之結構圖。其中粗線部分的螯化環表示安定的構形，細線部分的螯化環表示不安定的構形，打星號(＊)者代表甲基位於軸向位置。-----------10 圖 2-1 Mechanism of the non template effect.---------------------------14 圖 3-1 六種[Ni-(1, 7-CTH)]異構物結構圖，〝＋〞表示氫原子在NiN4平面上方；〝－〞表示氫原子在NiN4平面下方。〝＊〞表示軸向甲基。------------------------------------------------------------25 圖 3-2 (5, 7, 7, 12, 14, 14－六甲基－1, 4, 8,12－四氮環十四元環)鎳(Ⅱ)錯化合物M-N可能的IR震動模式。-----------------------32 圖 3-4 [α-Ni(rac-1,7-CTH)](ClO4) 2 IR光譜。-------------------------34 圖 3-5 [β-Ni(rac -1,7-CTH)](ClO4) 2 IR光譜。-------------------------35 圖 3-6 [γ-Ni(rac -1,7-CTH)](ClO4) 2 IR光譜。------------------------36 圖 3-7 [δ-Ni(rac -1,7-CTH)](ClO4) 2 IR光譜。-------------------------37 圖 3-8 [ε-Ni(rac -1,7-CTH)](ClO4) 2 IR光譜。-------------------------38 圖 4-1 Scheme of the internal conjugate base(ICB) effect in the coordination of ethylenediamine.---------------------------------43 圖 4-2 Configurational isomers of planar Ni(cyclam)2+.---------------53 圖 4-3 A plot of kobs vs [en]T for the reaction of[α-Ni(tet-b)]2+ withen (μ= 0.1 M, 25.0 ± 0.1℃). -------------------------------------60 圖 4-4 A plot of (kobs – kd) / [en] vs [H+] for the reaction of [α-Ni(tet-b)]2+ with en (μ= 0.1 M, 25.0 ± 0.1℃). ---------------61 圖 4-5 A plot of kobs vs [en]T for the reaction of Ni(tren)2+ with en (μ= 0.1 M, 25.0 ± 0.1℃).---------------------------------------------63 圖 4-6 A plot of (kobs – kd) / [en] vs [H+] for the reaction of Ni(tren)2+ with en (μ= 0.1 M, 25.0 ± 0.1℃).--------------------------------64 圖 4-7 A plot of kobs vs [en]T for the reaction of Ni([12]aneN4)2+ with en (μ= 0.1 M, 25.0 ± 0.1℃).--------------------------------------66 圖 4-8 A plot of (kobs – kd) / [en] vs [H+] for the reaction ofNi([12]aneN4)2+ with en (μ= 0.1 M, 25.0 ± 0.1℃).-----------67 圖 4-9 Ratio of the distribution of Ni(cyclam)2+ in aqueous solution at ionic strength μ= 0.1 M (NaClO4).------------------------------69 圖 4-10 Proposed mechanism for reaction of Ni(cyclam)2+ withbidentate ligands.----------------------------------------------------70 圖 5-1 ORTEP drawing of the [Ni([12]aneN4)(H2O)2]2+ cation. Hydrogen atoms are not shown for the sake of clarity. Probability ellipsoids are 30%-------------------------------------78 圖 5-2 ORTEP drawing of the molecular structure of [α-Ni(tet-b) (en)] (ClO4)2 along with the atom numbering scheme.-------------80 附錄 圖 A-1 ORTEP drawing of the molecular structure of [α-Ni(tet-b)(en) ] (ClO4)2 along with the atom numbering scheme.------------104 圖 A-2 ORTEP drawing of the molecular structure of [α-Ni(tet-b)(en)] (ClO4)2 along with the atom numbering scheme.------------105 圖 A-3 ORTEP drawing of the molecular structure of [α-Ni(tet-b)(en)] (ClO4)2 along with the atom numbering scheme.------------106 圖 A-4 ORTEP drawing of the molecular structure of [Ni(tren)(en)](ClO4)2 along with the atom numbering scheme.--------------118 表目錄 表 1-1 The abbreviation and nomenclature of tetra-aza ligands.------11 表 3-1 六種[Ni(1,7-CTH)(NCS)2]異構物之紅外線特性吸收光譜數據。-------------------------------------------------------------------28 表 3-2 六種異構物[β-Ni(meso-1,7-CTH)]2+，[α-Ni(rac-1,7-CTH)] 2+， [β-Ni(rac-1,7-CTH)] 2+，[γ-Ni(rac-1,7-CTH)] 2+，[δ-Ni(rac-1,7- CTH)] 2+及[ε-Ni(rac-1,7-CTH)] 2+遠紅外線光譜吸收數據。------------------------------------------------------------31 表 4-1 The pH range and selected wavelengths for the reactions of [α-Ni(rac-1,7-CTH)2+]，[Ni([12]aneN4)(en)]2+ and [Ni(tren)(en)2+] with en.-------------------------------------------------------55 表 4-2 Experimental observed rate constants for the [α-Ni(tet-b)]2+ with ethylenediamine at 25.0 ± 0.1℃ and μ= 0.1 M(NaClO4).-------------------------------------------------------------59 表 4-3 Rate constants for forward reaction (kf) and reverse reaction (kd) of[α-Ni(tet-b)]2+ with en at 25.0 ± 0.1℃ and μ= 0.1 M (NaClO4).-------------------------------------------------------------60 表 4-4 Rate constants for the reaction of[α-Ni(tet-b)]2+ with etheylenediamine at 25.0 ± 0.1℃ and μ= 0.1 M (NaCl).---61 表 4-5 Experimental observed rate constants for the Ni(tren)2+ withethylenediamine at 25.0 ± 0.1℃ and μ= 0.1 M (NaCl).-----62 表 4-6 Rate constants for forward reaction (kf) and reverse reaction (kd) of Ni(tren)2+ with en at 25.0 ± 0.1℃ and μ= 0.1 M (NaCl).----------------------------------------------------------------62 表 4-7 Rate constants for the reaction of Ni(tren)2+ with etheylenediamine at 25.0 ± 0.1℃ and μ= 0.1 M (NaCl).---64 表 4-8 Experimental observed rate constants for the Ni([12]aneN4)2+ with ethylenediamine at 25.0 ± 0.1℃ and μ= 0.1 M (NaCl). --------------------------------------------------------------------------65 表 4-9 Rate constants for forward reaction (kf) and reverse reaction (kd) of Ni([12]aneN4)2+ with en at 25.0 ± 0.1℃ and μ= 0.1 M (NaCl).-------------------------------------------------------------66 表 4-10 Rate constants for the reaction of Ni([12]aneN4)2+ with etheylenediamine at 25.0 ± 0.1℃ and μ= 0.1 M (NaCl).----67 表 4-11 Values of KOS for Various Combinations of Charged Reactions Calculated at 25℃ by Using the Modified Fuoss Equation---72 表 5-1 Selected structural data of [NiT(L)](ClO4)2.---------------------83 附錄 表 A-1 Crystal data and structure refinement for [α-Ni(tet-b)(en)] (ClO4)2.----------------------------------------------------------------94 表 A-2 Atomic coordinates (x104) and equivalent isotropic displacement parameters (Å2x 103) for [α-Ni(tet-b)(en)] (ClO4)2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.------------------------------------------95 表 A-3 Bond lengths [Å] and angles [°] for [α-Ni(tet-b)(en) ](ClO4)2.--------------------------------------------------------------------------97 表 A-4 Anisotropic displacement parameters (Å2x 103) for [α-Ni (tet-b)(en)](ClO4)2. The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ].-----------------------------------------------------------------100 表 A-5 Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for[α-Ni(tet-b) (en)] (ClO4)2.---------102 表 A-6 Crystal data and structure refinement for [Ni(tren)(en)](ClO4)2. ------------------------------------------------------------------------107 表 A-7 Atomic coordinates (x104) and equivalent isotropic displacement parameters (Å2x103) for [Ni(tren)(en)](ClO4)2. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.------------------------------------------------------------108 表 A-8 Bond lengths [Å] and angles [°] for [Ni(tren)(en)](ClO4)2.-----------------------------------------------------------------------------110 表 A-9 Anisotropic displacement parameters (Å2x103) for [Ni(tren)(en)](ClO4)2. The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ].----------------------------------------------------------------114 表 A-10 Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for [Ni(tren)(en)](ClO4)2.-------------116

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