臺灣博碩士論文加值系統

銅原子廣泛地存在生物體內，且銅金屬原子更是生物體內不同生化功能的主要因素。並且銅也是生物體中重要電子傳輸的載體，尤其大部份是以雙核銅的形式存在於自然界中。例如 dopamine ??-monooxygenase(D?浢)。在本論文中，合成一系列含有共軛的橋接配位子及含氮之三牙配位子的雙核銅一價錯合物。以過量的橋接配位子(i.e. pyrazine, 4,4’-bipyridine及 1,4-diisocyaobenzene)和[Cu(3,5-
dmTPM)(NCMe)]BF4合成出單核銅一價化合物[Cu(3,5-dmTPM)(pyrazine)]BF4 (1), 和[Cu(3,5-dmTPM)(4,4’-bipyridine)]BF4 (3) and [Cu(3,5-dmTPM)(1,4-
CNC6H4NC)]BF4 (5)。接著以等當量的單核銅一價化合物(1), (3), (5)和[Cu(3,5-dmTPM)(NCMe)]BF4合成出雙核銅一價化合物[Cu(3,5-dmTPM)]2(?? -pyrazine)(BF4)2 (2)及[Cu(3,5-dmTPM)]2(??-4,4´-bipyridine) (BF4)2 (4)。另外，[Cu(3,5-dmTPM)]2 (??-1,4- CNC6H4NC)](BF4)2 (6)與[Cu(TPMA)]2 (??-1,4-
CNC6H4NC)](BF4)2 (7)則以兩當量[Cu(3,5-dmTPM)(NCMe)]BF4或TPMA與一當量的1,4-diisocyaobenzenez方式合成。化合物(1)及化合物(2)在溶液中可經由變溫1H-NMR實驗觀察到橋接配位子pyrazine進行締結與解離的現象。單核銅一價化合物(5)和雙核銅一價化合物(2)、(4)及(7)已經由X-ray單晶繞射解出其分子結構。化合物(2)、(4)及(7)的雙銅間的距離分別近似D?浢氧化態和還原態的雙銅間距離(6.689Å, 10.981Å ,11.421Å)。由紅外光譜指出化合物(5), (6)及(7)的異氰基訊號比較接近D?浢上CuA的異氰基訊號。單核銅一價化合物(1), (3), (5)與雙核銅一價化合物(2), (4), (6)及(7) 進行電化學行為的研究與討論。在本論文中，化合物(1)~(7)的合成與鑑定可以提供對於銅一價含氮三牙配位子錯合物及銅蛋白的討論。

Copper is used widely as a metal cofactor to perform different function in biology. Biological electron transfer agents that feature copper are most typically dinuclear in nature, e.g. dopamine ??-monooxygenase(D?浢). In this work, we had synthesized a series of dicopper(I) complexes contain conjugated bridge ligand and tridenated ligand of N-donor. The mononuclear complexes [Cu(3,5-
dmTPM)(pyrazine)]BF4 (1), [Cu(3,5-dmTPM)(4,4’-bipyridine)]BF4 (3) and [Cu(3,5-dmTPM)(1,4-CNC6H4NC)]BF4 (5) were prepared by the reaction of excess ligands (i.e. pyrazine, 4,4’-dipyridyl and 1,4-diisocyaobenzene) with [Cu(3,5-
dmTPM)(NCMe)]BF4. The binuclear complexes [Cu(3,5-dmTPM)]2(?? -pyrazine)(BF4)2 (2), [Cu(3,5-dmTPM)]2(??-4,4´-bipyridine) (BF4)2 (4) were prepared by using equal molar ratio of [Cu(3,5-dmTPM)(NCMe)]BF4 and mononuclear complexes (1) or (3), respectively. In addition, [Cu(3,5-dmTPM)]2 (??-1,4- CNC6H4NC)](BF4)2 (6) and [Cu(TPMA)]2 (??-1,4-CNC6H4NC)](BF4)2 (7) were prepared with ratio 2:1 [Cu(3,5-dmTPM)(NCMe)]BF4 or TPMA and1,4-diiso-
cyanobenzene. The dissociative/associative behaviors of bridge pyrazine of complex (1) and (2) in solution were observed in variable temperature 1H-NMR spectrum. The mononuclear complex (5) and binuclear complex (2), (4), (7) also investigated via single crystal X-ray diffraction. The distances of two copper(I) centers of complexes (2), (4) and (7) were respectively similar to the oxidizing or reducing state of dopamine ??-monooxygenase (6.689Å, 10.981Å ,11.421Å). IR spectra indicated complexes (5), (6) and (7) were similar to CuA site of dopamine ??- monooxygenase in our model. Mononuclear complexes (1), (3), (5) and dinuclear complexes (2), (4), (6), (7) with symmetrically bridge ligands were studied by cyclic voltammetry and by UV-vis spetra。The synthesis and characterization of those compounds have provided fundamental knowledge about copper(I) complexes containing nitrogen donor ligand, necessary for a deeper understanding of the copper enzymes in particular as well as pyridyl and pyrazolyl complexes in general.

第壹章、 緒論………………………………………………………….1
1-1 簡介…………………………………………………………………1
1-2 含銅蛋白的介紹……………………………………………………4
1-3 含銅蛋白的電子傳遞………………………………………………9
1-3-1 CuA site模型化合物介紹………………………………………...10
1-3-2 CuB site模型化合物介紹………………………………………...19
1-4 研究目的…………………………………………………………...25

第貳章、 結果與討論…………………………………………...……...29
2-1化合物[Cu(3,5-dmTPM)(pyrazine)]BF4 (1)和[Cu(3,5-dmTPM)]2(??-
pyrazine)(BF4)2 (2)的合成反應.………………………...…….......29
2-2化合物[Cu(3,5-dmTPM)(4,4’-bipyridine)]BF4 (3)和[Cu(3,5-
dmTPM)(??-4,4’-bipyridine)]2(BF4)2 (4)的合成反應………….……41
2-3化合物[Cu(3,5-dmTPM)(1,4-CNC6H4NC)]BF4 (5) 和[Cu(3,5-
dmTPM)]2 (??-1,4-CNC6H4NC)](BF4)2 (6)的合成反應…..……...…48
2-4化合物[Cu(TPMA)]2 (??-1,4-CNC6H4NC)](BF4)2 (7)的合成反應…55
2-5三吡咯銅一價錯合物的結構比較….….…......................................61

第叁章、 實驗部分……………………………………………………..65
3-1試藥來源及前處理…………………………………...…………….65
3-2儀器部分………………………………………………...………….67
3-3 實驗步驟………………………………………………….………..70
3.3.1 [Cu(3,5-dmTPM)(pyrazine)]BF4 (1)的合成……………………...70
3.3.2 [Cu(3,5-dmTPM)]2(??-pyrazine)(BF4)2 (2)的合成……………..…71
3.3.3 [Cu(3,5-dmTPM)(4,4’-bipyridine)]BF4 (3) 的合成….….….…....72
3.3.4 [Cu(3,5-dmTPM)]2 (??-4,4’-bipyridine)](BF4)2 (4)的合成…..……73
3.3.5 [Cu(3,5-dmTPM)(1,4-CNC6H4NC)](BF4)2 (5)的合成…………...74
3.3.6 [Cu(3,5-dmTPM)]2 (??-1,4-CNC6H4NC)](BF4)2 (6)的合成………75
3.3.7 [Cu(TPMA)]2 (p-CNC6H4NC)](BF4)2 (7)的合成...........................77

參考文獻………………………………………………………………..80

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