臺灣博碩士論文加值系統

本研究合成一系列錳、硫和磷錯合物模擬生物酵素探討與氧氣的反應性。其中雙硫橋接雙核錳的[PPN]2[MnII2(TMSPS3)2] (1)由二氯化錳、[PPN]Cl和Li3TM-SPS3合成，其與過量DABCO反應轉變成單核[PPN][MnII(DABCO)(TMSPS3)] (2)。利用UV-vis光譜儀探討變溫實驗指出雙核1在存有DABCO的環境與單核2之間的平衡反應，其低溫傾向單核2的生成。針對1和2與雙邊鍵結的四價過氧化物[PPN][MnIV(η2-O2)TMSPS3] (3)反應產生氧橋接雙錳的[PPN]2[MnIII2(μ-O)(TMSPS3)2](4)，化合物4能更進一步的被水分子質化生成[PPN][MnIII(OH)(TMS-PS3)](5)。電化學顯示1和2的氧化電位(MnIII/MnII)之間的位移，並指出兩者皆有被氧氣氧化的潛力；5則突顯高還原電位更難以誘導催化反應的發生。在不同的相態探討1和2與氧氣活化，晶體的2與乾燥的氧氣反應幾乎完全轉換成四價過氧基的3，這指出完整的固相轉換以及氧氣的兩電子的還原。在溶液狀態下受氧氣濃度與擴散效應影響，導致3和 4兩種產物生成比例不同。

　　In this studies, we synthesized a series of manganese complex with sulfur and phosphorus donor atoms. A thiolate-bridged binuclear [PPN]2[(MnII(TMSPS3))2] (1) prepared from the reaction of MnCl2/ [PPN]Cl and Li3[TMSPS3] converts into a mononuclear [PPN]-[MnII(TMSPS3)(DABCO)] (2) in the presence of excess amounts of DABCO. Variable temperature studies of solution containing 1 and DABCO by UV–vis spectroscopy indicate that 1 and 2 exist in significant amounts in equilibrium and mononuclear 2 is favored at low temperature. Treatment of 1 and 2 with a O2-side-on-bound [PPN][MnIV(η2-O2)TMSPS3] (3) produces a mono-oxo-bridged dimeric [PPN]2[MnIII2(μ-O)(TMSPS3)2](4). Reaction of 4 with H2O can generate complex [PPN][MnIII(OH)(TMSPS3)](5). The electrochemistry of 1 and 2 reveal anodic peak(s) for MnIII/MnII redox couple at shifted potentials against Fc/Fc+, indicating that both complexes can be oxidize by dioxygen. The O2 activation mediated by 1 and 2 is investigated in both solution and the solid states. Crystals of 2 rapidly reacts with air or dry O2 to generate the Mn(IV)-peroxo 3 in nearly quantitative yield, revealing a clean solid-to-solid transformation and two-electron reduction of O2. Oxygenation of 1 or 2 in solution, however, is affected by diffusion and transient concentration of dioxygen in the two different substrates, leading to generation of 3 and 4 in variable yield ratio

第一章 緒論
1-1 氧氣　 1
1-2 第二光系統與氧氣的釋放　 4
1-3 Ib型核醣核苷酸還原酶與酪氨酸自由基誘導因子　 6
1-4 錳氧模擬化合物文獻探討　 9
1-5 研究方向　 13
第二章 實驗部分
2-1 一般實驗　 14
2-2 儀器　 14
2-3 藥品　 15
2-4 化合物的合成與性質鑑定
2-4-1 配位基Tris(2-thiol-3-trimethylsiylphenyl)phosphine, (TMSPS3H3)的合成　 18
2-4-2 化合物[PPN]2[MnII2(TMSPS3)2] (1)的合成　 19
2-4-3 化合物[PPN][MnII(DABCO)(TMSPS3)] (2)的合成　 19
2-4-4 化合物[PPN][MnIV(η2-O2)(TMSPS3)] (3)的合成　 20
2-4-5 化合物[PPN]2[MnIII2(μ-O)(TMSPS3)2] (4)的合成　 20
2-4-6 化合物 1 與 3 的反應　 21
2-4-7 化合物 1 與 3 在含有PPh3的反應　 21
2-4-8 化合物 2 與PhIO反應　 21
2-4-9 化合物 1 與氧氣反應　 22
2-4-10 化合物 2 與氧氣反應　 22
2-4-11 化合物 1 與 2 的固相氧化　 23
2-4-12 化合物[PPN][MnIII(OH)(TMSPS3)] (5)的合成　 23
2-4-13 化合物 5 與2,6-di-tbu-4-R-PhOH(R=OMe)的反應　 24
2-4-14 平衡常數的測定　 24
第三章 結果與討論
3-1 含錳(II)化合物的合成、結構與性質鑑定　 25
3-2 含錳(III)化合物的合成、結構與性質鑑定　 31
3-3 含錳(II)化合物與氧氣的反應性　 39
3-4 錯合物的分子結構探討　 47
第四章 結論　 55
參考文獻　 57

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