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博碩士論文 etd-0721104-211306 詳細資訊
Title page for etd-0721104-211306
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
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
74
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
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
統計
Statistics
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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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