臺灣博碩士論文加值系統

在此研究中，我們用一個新的合成方法，將DCP直接於硫化氫氣體下加熱，可得到含硫橋基雙二氮雜菲化合物DTPP，並由元素分析、質譜及核磁共振光譜的量測確定其結構。另外經由電子吸收光譜酸鹼滴定的研究，亦求得其酸解離常數為pKa2 = 4.48，pKa1由推測為-1.21。
DTPP配位子和氯化亞鐵、亞鈷、鎳、銅進行反應，可得到鐵、鈷、鎳、銅錯合物。由元素分析、質譜及核磁共振光譜的量測，鈷、鎳、銅錯合物為二價形式存在，且軸配位上為氯離子；而鐵錯合物為一氯架橋之雙核錯合物，在電子吸收光譜可觀察到此結構在約650 nm處的特徵吸收，而在77 K電子自旋共振光譜上，鈷及銅錯合物均有三個g值，由g值的位置我們可判斷鈷及銅錯合物為拉長軸的八面體結構。由X-ray晶體繞射法解出鎳和銅錯合物的晶體結構，均為六配位結構，與光譜的推測相同。另藉由電子吸收光譜酸鹼性質的研究，得到鈷錯合物之鹼合成常數KL1 = 1.02 ×105。而鐵及銅錯合物分別在中性及鹼性下發生單核及雙核物種的平衡及氫氧基取代反應。錯合物的軸配位可以配位力較強的鹼置換，使用了imidazole、pyridine和4-methylpyridine分別得到了雙取代及單取代的產物[Co(DTPP)(Im)2]Cl2、[Co(DTPP)(Py)Cl]Cl及[Co(DTPP)(4-MePy)Cl]Cl，而其生成常數為7.82 ×104、12.5及125。錯合物的電化學行為藉由不同的溶劑系統來進行。鈷錯合物於氮氣下水溶液中分別可觀察出0.55 V (CoIII/CoII)及-0.35 V (CoII/CoI)兩組可逆的氧化還原峰，在氧氣下則出現了接氧氣的催化電流；銅錯合物於水溶液中分別可觀察出-0.21 V (CuII/CuI)可逆的氧化還原峰；而鐵錯合物於碳酸丙烯溶液中分別可觀察出0.16 V (FeIIIFeIII/FeIIIFeII)、-0.92 V (FeIIIFeII/FeIIFeII)兩組可逆的氧化還原峰及還原峰在-0.52 V，而氧化峰在0.21 V的近可逆氧化還原峰。而在-1.35 V不可逆的氧化峰則為配位子的還原峰。

We synthesize a new dithiotetraazamacrocyclic ligand(DTPP). We observed the acid dissociation constants of H2DTPP2+ from electronic absorption spectra. The pKa2 of the ligand was 4.48, but the pKa1 of the ligand was —1.21 by prediction.
Its iron(II), cobalt(II), nickel(II), and copper(II) complexes have been synthesized and characterized by EA, MASS, and NMR, respectively. The 77K EPR spectra of [Co(DTPP)Cl2] powder and [Cu(DTPP)Cl2] solution showed three g values, according the g values we can decided the structure is z-elongation octahedral. The crystals of nickel(II) and copper(II) complexes was charactized by X-ray diffraction analysis and all of them are six-coordination. The pH dependent changes with isobestic point resulted in the spectroscopic titration of the complexes was observed. The KL of the cobalt(II) complex with a hydroxy group was 1.02 ×105, and we purposed that iron(II) and copper(II) complexes occurred the equilibrium of monomer and dimer and hydroxy group substitution, respectively. We used imidazole, pyridine, and 4-methylpyridine to substitution axial ligand, and found the formation constant of [Co(DTPP)(Im)2]Cl2, [Co(DTPP)(Py)Cl]Cl, and [Co(DTPP)(4-MePy)Cl]Cl was 7.82 ×104, 12.5, and 125, respectively. The cyclic voltammograms(CV) of the complexes, the cobalt(II) complex showed two reversible redox peaks in water at 0.55 V (CoIII/CoII) and —0.35 V (CoII/CoI), and the copper(II) complex showed a reversible peak in water at —0.21 V (CuII/CuI).The iron(II/III) complex showed two reversible redox peaks, a quasi-reversible redox peak and a irreversible reductive peak in propylenecarbonate at 0.16 V (FeIIIFeIII/FeIIIFeII), -0.92 V (FeIIIFeII/FeIIFeII) and —1.35 V (ligand center).

第一章 緒論
1-1 大環化合物………………………………………………………1
1-2 雙二氮雜菲大環化合物及其回顧………………………………2
1-3 含硫及含氮橋基雙二氮雜菲大環化合物的差異………………4
第二章 含硫橋基雙二氮雜菲配位子(DTPP)的合成與性質研究
實驗部分
試劑與藥品………………………………………………………5
合成方法…………………………………………………………5
物理方法測量……………………………………………………8
結果與討論
2-1 化合物的合成……………………………………………………10
2-2 光譜研究…………………………………………………………13
2-2-1 核磁共振光譜
2-2-2 紅外光譜
2-2-3 電子吸收光譜
2-3 酸鹼性質…………………………………………………………17
2-4 電化學性質………………………………………………………23
第三章 含硫橋基雙雜菲鐵、鈷、鎳、銅錯合物的合成與性質研究
實驗部分
試劑與藥品………………………………………………………25
合成方法…………………………………………………………25
物理方法測量……………………………………………………27
結果與討論
3-1 錯合物的合成……………………………………………………29
3-2 分子結構與晶體結構……………………………………………29
3-2-1 鎳錯合物
3-2-2 銅錯合物
3-3 光譜研究…………………………………………………………48
3-3-1 核磁共振光譜
3-3-2 紅外光譜
3-3-3 電子吸收光譜
3-3-4 電子自旋共振光譜
3-4 酸鹼性質…………………………………………………………58
3-4-1 鈷錯合物的酸鹼性質
3-4-2 鎳錯合物的酸鹼性質
3-4-3 銅錯合物的酸鹼性質
3-4-4 鐵錯合物的酸鹼性質
3-5 軸配位性質………………………………………………………67
3-6 電化學性質………………………………………………………73
3-6-1 鈷錯合物
3-6-2 鎳錯合物
3-6-3 銅錯合物
3-6-4 鐵錯合物
第四章 結論…………………………………………………………83
參考資料………………………………………………………………85
圖附錄…………………………………………………………………87

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