臺灣博碩士論文加值系統

本論文第一部分主要內容是以DFT之PBEPBE/6-31G(d,p)+LanL2DZ計算CpRu(PH3)2Cl (1)形成含氮六員環釕金屬CpRu(=C(CH2 (Ph))NHCH2-C(Ph)CH)(PH3) (2)與含氮四員環釕CpRu(=C(CH2(Ph)) N(CH3)C=CH(Ph))(PH3) (3)的可能性及反應機構的推測，結果發現對其反應機構進行計算所得到的能量是符合機構推導的，這也表示Cp雖然在立障及推電子的能力上雖然不如Tp，但四員環及六員環結構會是與甲胺及苯乙炔的產物。
第二部分是利用TpRu(PPh3)2Cl (4)與2-aminopyrimidine反應，經一系列實驗得到TpRu(PPh3)(2-aminopyrimidine)Cl (5)的結構，再利用化合物5作為起始物在不同溶劑的條件下與苯乙炔反應，以期望得到亞乙烯基的結構。

In this study, our research objectives are focused on designing novel ruthium complexes and understand the relations between catalysis mechanism and chemical structure. For two-year efforts, there are two main research achievement as shown below：
(a) Treatment of TpRu(PPh3)2Cl (4) with 2-aminopyrimidine afforded to TpRu(PPh3)(2-aminopyrimidine)Cl (5). The structures of complex 5 have been determined by X-ray diffraction analysis.
(b) We also have used to theoretical calculations for the reaction of ruthenium complex to support our purposed mechanism.

目錄 I
附圖目錄 IV
附表目錄 VII
化合物編號及頁碼 VIII

第一章 緒論 1
§1-1 配位基的選擇 2
§1-2 亞乙烯基中間體 4
§1-3 2-胺基嘧啶 9
§1-4 研究動機 10

第二章 理論計算 11
§2-1 理論計算研究 11
§2-2 計算方法 11
§2-3 基組(Basis Set) 13
2-3-1 6-31G(d,p) 13
2-3-2 LanL2dz 14

第三章 結果與討論 15
§3-1 計算CpRu(PH3)2Cl(1)與苯乙炔及甲胺的反應 15
§3-2 CpRu(=C (CH2 (Ph))NHCH2C(Ph)=CH)(PH3) (2)的反應機構推測 17
3-2-1 化合物1到CpRu(= C=C(Ph)H) (PH3)2 (1a)理論計算 19
3-2-2 化合物1a到CpRu(= C(C H2(Ph))(NHCH3)) (PH3)2(1b )理論計算 21
3-2-3 化合物1b到CpRu(= C(C H2(Ph)(NHCH3) (=C=C(Ph)H)(PH3)(1c )理論計算 22
3-2-4 化合物1c到CpRu(=C (CH2(Ph))NHCH2C(Ph)=CH)(PH3) (2)理論計算 24
§3-3 CpRu (=C(CH2(Ph))N(CH3)C(=CH(Ph)))(PH3)(3)的反應機構 28
3-3-1 化合物1a到CpRu(= C(C H2(Ph))(NHCH3)) (PH3)2 (2b)理論計算 30
3-3-2 化合物2b到CpRu(=C(CH2(Ph))(NHCH3))(=C=CH(Ph))(PH3)(2c)理論計算 31
3-3-3 化合物2c到CpRu(= C(CH2(Ph))N(HCH3))C(CH(Ph)) (PH3)(2d)理論計算 33
3-3-4 化合物2d到CpRu(= C(CH2(Ph))N(CH3) C(CH2(Ph)))(PH3)(2e)理論計算 36
3-3-5 化合物2e到CpRu(= C(C H2(Ph))N(CH3)C(=CH(Ph)))(PH3) (3)理論計算 38
§3-4 化合物1的總反應 41

第四章 釕金屬化合物與2-胺基嘧啶在甲苯下的反應 42
§4-1 TpRu(PPh3)2Cl (4) 的合成 42
§4-2 TpRu(PPh3)(2-aminopyrimidine) Cl (5)的合成 45
4-2-1 圖譜分析 45
4-2-2 晶體結構 49
§4-3 實驗總結 50

第五章　含氮釕金屬化合物後續反應 52
§5-1 TpRu(PPh3)(2-aminopyrimidine)Cl (5)的後續反應 52
§5-2 化合物5與苯乙炔於甲醇下反應 52
5-2-1 圖譜分析 53
§5-3 化合物5與苯乙炔於甲苯下反應 54
5-3-1 圖譜分析 54

第六章 結論 56

第七章 實驗器材及實驗合成 58
§7-1 藥品及器材 58
7-1-1 實驗藥品 58
7-1-2 實驗器材 59
§7-2 實驗合成 59
7-2-1 TpRu(PPh3)(2-aminopyrimidine) Cl (5)的合成 59

參考文獻 60

附錄 63

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