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博碩士論文 etd-0630113-150246 詳細資訊
Title page for etd-0630113-150246
論文名稱
Title
開環富勒烯與三釕羰基金屬簇之反應性研究
Reactions of Open-Cage Fullerene with Triruthenium Carbonyl Cluster
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
91
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
2013-07-25
繳交日期
Date of Submission
2013-07-30
關鍵字
Keywords
三釕羰基金屬簇、碳六十、開環富勒烯
Fullerene, Open-Cage Fullerene, Triruthenium Carbonyl Cluster
統計
Statistics
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The thesis/dissertation has been browsed 5664 times, has been downloaded 331 times.
中文摘要
本論文主要是研究碳六十開環化合物與三釕羰基金屬簇之反應研究。利用具有十二圓環開環富勒烯 C80H14N2O2 (2) 與 Ru3(CO)12 於氯苯 (Chlorobenzene) 下反應得到一個具有八圓環的開環富勒烯錯合物 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3),接著利用化合物 3 進行熱裂反應得到一個具有十一圓環開環富勒烯雙釕錯合物 HRu2(CO)3(μ2, η7-(C63N(C6H4)PhPy)) (4),最後藉由 X-Ray、IR、MASS、1H及13C NMR、UV-Vis、電化學來對其作一系列的鑑定與探討。
Abstract
Reaction of C80H14N2O2 (2) and Ru3(CO)12 in refluxing chlorobenzene affords Ru3(CO)8(μ2, η7-(C63NO2Ph2Py)) (3). Compound 3 apparentily arises from C-C bond activation of 2 to generate an diol ligand bridging motif. In contrast, compound 4 is produced by C-H / C-O activation insertion of one ruthenium atom into a pentagonal ring of 3, together with the Ru3 cluster fragmentation. Complexes 3 and 4 have been characterized by IR, NMR, UV-Vis, CV, Mass spectroscopies, and single-crystal X-ray diffraction study.
目次 Table of Contents
摘要 (中): ..........................................................................................................................i Abstract ................................................................................................................... ii
謝誌 ......................................................................................................................... iii
目錄 ..........................................................................................................................iv
圖目錄 .......................................................................................................................vi
表目錄 .......................................................................................................................viii
第壹章 緒論 ............................................................................................................... 1
1.1 碳六十介紹 ...........................................................................................................1
1.2 碳六十與金屬的反應 ............................................................................................. 3
1.3 開環富勒烯介紹 ................................................................................................... 4
1.4 開環富勒烯與金屬的反應動機 ................................................................................ 9
第貳章 結果與討論 ......................................................................................................10
2.1 合成化合物 C80H14N2O2 (2)................................................................................. 10
2.2 化合物 C80H14N2O2 (2)與Ru3(CO)12反應 ............................................................. 12
2.3 化合物 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3)之鑑定 ................................................13
2.4 化合物 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3) 之熱裂反應 ........................................ 24
2.5 化合物 HRu2(CO)3(μ2, η7-(C63N(C6H4)PhPy)) (4) 之鑑定 ........................................ 25
2.6 化合物 (5) 之鑑定 ................................................................................................. 35
2.7 化合物 (6) 之鑑定 ................................................................................................. 35
2.8 化合物 3 及化合物 4 的結構探討 ............................................................................ 36
2.9 化合物 1-4 的紫外光-可見光光譜的探討 ............................................................. 37
2.10 化合物 1-4 的電化學探討 .................................................................................. 39
2.11 結論 ................................................................................................................. 40
第參章 實驗部分 .........................................................................................................41
3.1 使用儀器 ............................................................................................................. 41
3.2 試藥來源及前處理 ................................................................................................ 42
3.3 C80H14N2 (1) 的合成 ........................................................................................... 43
3.4 C80H14N2O2 (2) 的合成 ....................................................................................... 43
3.5 C80H14N2O2 (2) 與Ru3(CO)12的反應 .................................................................... 44
3.5.1 C80H14N2O2 (2) 空白反應: ................................................................................ 45
3.5.2 Ru3(CO)12 空白反應: ........................................................................................ 45
3.6 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3) 的熱裂反應 .................................................. 46
3.6.1 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3) 的固態熱裂反應: ....................................... 46
3.6.2 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3) 的液態熱裂反應: ....................................... 47
3.7 HRu2(CO)3(μ2, η7-(C63N(C6H4)PhPy)) (4) 固態熱裂反應: ....................................... 47
3.8 HRu2(CO)3(μ2, η7-(C63N(C6H4)PhPy)) (4) 液態熱裂反應: ....................................... 47
3.9 循環伏安法的測定 ................................................................................................ 48
參考文獻 .................................................................................................................. 49
附錄一 ...................................................................................................................... A-1
附錄二 .................................................................................................................... A-14
附錄三 .................................................................................................................... A-26
附錄四 .................................................................................................................... A-27
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