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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 劉緒宗(Shiuh-Tzung Liu) | |
dc.contributor.author | Yu-Hao Wang | en |
dc.contributor.author | 王昱皓 | zh_TW |
dc.date.accessioned | 2021-06-17T04:25:46Z | - |
dc.date.available | 2019-08-18 | |
dc.date.copyright | 2018-08-18 | |
dc.date.issued | 2018 | |
dc.date.submitted | 2018-08-14 | |
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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/70318 | - |
dc.description.abstract | 多牙氮配位基2,7-bis(2-pyridyl)-1,8-napthyridine (bpnp)是具有四個吡啶結構的配體,其多金屬錯合物已被廣泛合成,並應用在催化反應。在bpnp的雙金屬錯合物中,金屬之間的距離可以在約3 Å左右,使其金屬之間可以有鍵結的可能;在本篇工作中,嘗試以鈀(0)與鈀(II)之金屬前驅物,希望合成出金屬鍵架構的錯合物。遂利用bpnp與零價前驅物Pd2(dba)3以及二價前驅物PdCl2(PhCN)2在二氯甲烷中反應,卻意外地獲得具有C2對稱性的參鈀金屬錯合物[Pd3(bpnp)2Cl2]Cl2 (Pd3)。它在水與甲醇類的溶解度極高,因此在此溶劑將此錯合物作為催化劑,在最佳化條件之下,炔類分子可以被氫化而得到相對應的順式烯類為主產物。
其中以四氫呋喃與水作為共溶劑,並在30℃且1 atm之條件下氫化,二苯基乙炔(diphenylacetylene)可以成功轉化爲反式二苯基乙烯(cis-1,2-diphenylethene),只有非常少量的烯類被過度氫化成飽和烴。然而如果增加氫氣壓力或是提高反應溫度,也能將烯類氫化至烷類。除此之外,稍微修改反應條件後,此催化劑也能將疊氮化物(azide)氫化而得到相對應的胺類(amine)。本方法具有溫和的反應溫度、低催化劑量、短時間,以及方便的後處理等優點。 最後本篇工作使用密度泛函理論(DFT, Density Functional Theory)進行理論計算。在泛含以及基底函數組的選用上,非金屬原子的部分使用B3LYP/6-31+G(d,p),而鈀原子則使用B3LYP/LANL2DZ,以此針對反應機制進行了詳細地探討。 | zh_TW |
dc.description.abstract | 2,7-bis(2-pyridyl)-1,8-napthyridine (bpnp) is a tetra-pyridinyl ligand, which is capable of accommodating dinuclear species. In our work, we have obtained a palladium complex chelated with bpnp in a trimetallic fashion. Complexation of bpnp with equal molar amount of Pd2(dba)3 and (PhCN)2PdCl2 in CH2Cl2 at ambient temperature, a complex [Pd3(bpnp)2Cl2]Cl2 with C2 symmetry was obtained. This tri-palladium complex, upon activated by NH3-BH3, was found to be catalytic active on hydrogenation of unsaturated hydrocarbons particularly for the semi-hydrogenation of alkyne into cis-alkenes. By manipulating reaction conditions, alkynes molecules can be converted into the corresponding Z-alkenes selectively. Typically, diphenylacetylene was transferred into cis-1,2-diphenylethene in THF/H2O at 30℃ under 1 atm of hydroden gas in 92% yield, accompanied with a minor amount of over-hydrogenated byproduct. Further reduction to alkanes can be achieved under a higher pressure of hydrogen or at raising temperature. Furthermore, other functional groups such as arylnitrile and azide can be hydrogenated to the corresponding amine by modification of the conditions slightly. This protocol has several advantages such as mild conditions, low catalyst loading, short reaction time, and convenient workup. The reaction mechanism was investigated by DFT calculation at the levels of B3LYP/6-31+G(d,p) and B3LYP/LANL2DZ. Furthemore, the use of tri-palladium complex in reduction of bicarbonate under various mild conditions was investigated. | en |
dc.description.provenance | Made available in DSpace on 2021-06-17T04:25:46Z (GMT). No. of bitstreams: 1 ntu-107-R05223121-1.pdf: 7052210 bytes, checksum: 9df42fe9a0a9113cc171d983add17b8a (MD5) Previous issue date: 2018 | en |
dc.description.tableofcontents | 誌謝 i
摘要 ii ABSTRACT iii 目錄 iv 附圖目錄 vi 附表目錄 vii 流程目錄 viii 第一章 緒論 1 1.1 多牙氮配位基錯合物及其催化應用 1 1.2 參鈀金屬團簇錯合物 4 1.3 炔類選擇性還原至烯類 7 1.4 研究目的 13 第二章 多牙氮配位基及金屬錯合物之合成 15 2.1 多牙氮配位基bpnp之合成 15 2.2 多牙氮配位基bppa以及bbppa之合成 16 2.3 參鈀金屬錯合物Pd3之合成與鑑定 17 2.4 雙銅金屬錯合物Cu2之合成 22 第三章 氫分子對炔類之順式加成反應 23 3.1 各類活化劑之反應性測試 23 3.2 以硼烷氨作為活化劑進行最佳化 24 3.3 反應對其他官能基之耐受性 26 3.4 與其他鈀金屬錯合物催化性質之比較 27 3.5 氫氣對炔類之順式加成反應之機構探討 31 3.6 以密度泛涵理論計算進行反應機構探討 33 第四章 其他催化反應之應用 43 4.1 類之還原反應 43 4.2 氮化合物之還原反應 43 4.3 氧化碳/碳酸氫根/碳酸根之還原反應 44 第五章 結論 51 第六章 實驗部分 53 6.1 測試儀器 53 6.2 試劑來源 54 6.3 實驗操作 54 6.4 實驗步驟及數據 55 參考文獻 70 附錄一 75 | |
dc.language.iso | zh-TW | |
dc.title | 以參鈀金屬錯合物催化氫分子對炔類之順式加成反應 | zh_TW |
dc.title | Z-Selective Semi-Reduction of Alkynes with Molecular Hydrogen Catalyzed by a Tri-Palladium Complex | en |
dc.type | Thesis | |
dc.date.schoolyear | 106-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 鄭原忠(Yuan-Chung Cheng),詹益慈(Yi-Tsu Chan),陳竹亭(Jwu-Ting Chen) | |
dc.subject.keyword | 鈀錯合物,有機金屬,缺類還原, | zh_TW |
dc.subject.keyword | Alkynes,Semi-Reduction,Palladium Complex, | en |
dc.relation.page | 105 | |
dc.identifier.doi | 10.6342/NTU201802582 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2018-08-15 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
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