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論文名稱 Title |
含亞胺-比咯多螯合基配位化學之研究 Coordination Chemistry of Multidentate Pyrrolylaldiminate Ligands |
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系所名稱 Department |
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畢業學年期 Year, semester |
語文別 Language |
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學位類別 Degree |
頁數 Number of pages |
74 |
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研究生 Author |
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指導教授 Advisor |
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召集委員 Convenor |
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口試委員 Advisory Committee |
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口試日期 Date of Exam |
2004-06-10 |
繳交日期 Date of Submission |
2004-07-21 |
關鍵字 Keywords |
席夫氏鹼、醯胺、比咯、鉿、亞胺、螯合、錳、鎳、鎂、鋁、鋯 Zirconium, phosphorous ylide., imine, Schiff Base, pyrrole, amide, Magnesium, Manganse, chelate, Alumium, Nickel, Hafnium |
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統計 Statistics |
本論文已被瀏覽 5626 次,被下載 0 次 The thesis/dissertation has been browsed 5626 times, has been downloaded 0 times. |
中文摘要 |
以5-tert-butylpyrrole-2-carbaldehyde當作起始物,分別與2,6-diisopropylaniline N,N-dimethylethylenediamine,以及ethylenediamine進行縮合反應,分別得到bi-、tri-、and tetradentate pyrrolylaldimine ligand precursors。這些中性的配位基前驅物,與我們所選擇的金屬化合物,進行配位化學的反應,包括:Zirconium,Hafnium, Nickel, Manganse,Magnesium,Alumium等。再經由核磁共振光譜,高解析質譜,X-ray單晶繞射,和元素分析的鑑定,確定了預期中錯化物的組成和結構。 |
Abstract |
none |
目次 Table of Contents |
壹、緒論 1 貳、實驗部分 4 一、儀器 4 二、藥品及純化 6 三、實驗步驟 11 1.合成5-tert-butyl-2-pyrrolecabaldehyde 11 2.合成5-tert-butyl-2-[(2,6-diisopropylphenylaldimino]- pyrrole;H[L1] 12 3.合成Na[L1]thf 12 4.合成[L1]HfCl4Li(OEt2)2 13 5.合成[L1]Ni(η3-CH2CMeCH2) 14 6.合成N-(2-dimethylaminoethyl)-5-tert-butyl-pyrrol-2 -ylaldimine;H[L2] 16 7.合成[L2]AlMe2 17 8.合成[L2]AlEt2 18 9.合成[L2]AlCl2 19 10.合成Zn[L2]2 20 11.合成N,N-ethylenedi-(5-tert-butylpyrrol-2- ylaldimine);H2[L3] 21 12.合成[L3]2Mg2 22 13.合成[L3]2Zn2 23 14.合成{[L3]Mn}2 24 15.合成[L3]ZrCl2 25 叁、結果與討論 27 1.配位基5-tert-butyl-2-[(2,6-diisopropylphenyl)aldimino] pyrrole; [L1]H (bi-dentate ligand)及其錯化物的合成與性質探討 28 2.配位基N-(2-dimethylaminoethyl)-5-tert-butyl-pyrrol-2 -ylaldimine;[L2]H (tri-dentate ligand)及其錯化物的合成與性質探討 34 3.配位基N,N’-ethylenedi-(5-tert-butyl-pyrrol-2-ylaldimine); [L3]H2 (tetra-dentate ligand)及其錯化物的合成與性質探討 37 肆、結論 44 伍、未來展望 45 陸、參考文獻 46 柒、附錄 52 1.合成prop-2-ynyltripheneylphosphonium bromide (1) 54 2.合成2-anilinoprop-1-enyltriphenylphosphonium bromide (2a) 55 3.合成2-(2,6-dimethylanilino)-prop-1-enyltriphenylphos phonium bromide(2b) 56 4.合成2-(2,6-diisopropylaniline)-prop-1-enyltriphenylphos- phonium bromide (2c) 59 5.合成2-(tert-butylamino)-prop-1-enyltriphenylphosphonium bromide (2d) 62 6.合成3a 65 7.合成3b 68 8.合成3c 71 9.合成3d 74 圖目 圖一 含氮雙芽配位基 1 圖二 錯化物[2-C4H3N(CH= NR)]2TiCl2 (R=C6H5, cyclo-C6H11) 2 圖三 本文所採用的配位基由左至右,分別為二牙(bi-dentate)、 三牙 (tri-dentate)、四牙(tetra-dentate)配位基。 3 圖四 合成二牙(bidentate)、三牙(tridentate)、四牙(tetradentate)配位基 27 圖五 含[L1]-配位基的Zr、Hf 、Ni錯化物 30 圖六 [L1]HfCl4Li(OEt2)2的分子結構、鍵長、及鍵角。 31 圖七 [L1]Ni(η3-CH2CMeCH2)的分子結構、鍵長、及鍵角。 33 圖八 含[L2]-配位基的Al、Zn錯化物 36 圖九 含[L3]2-配位基的Mg、Zn、Mn、Zr錯化物 39 圖十 [L3]2Mg2的分子結構、鍵長、及鍵角。 40 圖十一 Cu2L2、Mn2L2 (L=N,N’-ethylenedi-(pyrrol-2-ylaldiminate))、Mg2[L3]2 41 圖十二 [L3]2Mn2 的分子結構、鍵長、及鍵角。 43 圖十三 Shell higher-olefines process (SHOP) 圖十四 合成2-aminoprop-1-enyltriphenylphosphonium bromides、phosphorous ylides化合物及預期中的Ni衍生物 52 圖十五 2b的分子結構、鍵長、及鍵角。 58 圖十六 2c的分子結構、鍵長、及鍵角。 61 圖十七 2d的分子結構、鍵長、及鍵角。 64 圖十八 3a的分子結構、鍵長、及鍵角。 67 圖十九 3b的分子結構、鍵長、及鍵角。 70 圖二十 3c的分子結構、鍵長、及鍵角。 73 |
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