臺灣博碩士論文加值系統

將 pyrrole、 oxalyl chloride 和N,N-dimethylformaldehyde 利用Vilsmeier-Haack 反應；接著加入AlCl3和 Me3CCl行Friedel-Crafts alkylation 反應可得產物5-tert-butylpyrrole-2-carbaldehyde。將5-tert-butylpyrrole-2carbaldehyde 和2,6-diisopropylaniline經由縮合反應脫水得到配位基 5-tert-butyl-2-[(2,6-diisopropylphenyl)- aldimino]- pyrrole (HL)。將配位基(HL) 和MgnBu2 反應可得到二個配位基和鎂金屬鍵結的白色結晶狀的固體產物，錯合物MgL2 (1)。將配位基鋰鹽直接和一當量的ZrCl4 或AlCl3 反應得到一個配位基和鋯或鋁金屬鍵結的產物。錯合物ZrLCl4Li(OEt2)2 (2)及錯合物AlLCl2 (3)。將錯合物3和兩當量的MeMgBr 反應可得到錯合物AlLMe2 (4)。所合成出來的錯合物1、2、3、4可由NMR光譜證明，並利用X光單晶繞射鑑定出錯合物1、2、3、4的立體結構。

The Vilsmeier-Haack reaction of pyrrole with oxalyl chloride and N,N-dimethylformaldehyde followed by Friedel-Crafts alkylation with Me3CCl in the presence of AlCl3 afforded 5-tert-butylpyrrole-2- carbal- dehyde in high yields. Condensation reactions of 5-tert-butylpyrrole-2- carbaldehyde with 2,6-diisopropylaniline produced 5-tert-Butyl-2-2[(2,6- diisopropylphenyl)aldimino]pyrrole (HL). Protonolysis of MgnBu2 with HL yielded the bis(iminopyrrolate) complex MgL2 (1) as a colorless crystalline solid. In situ lithiation of HL followed by addition of one equivalent of ZrCl4 or AlCl3 led to the mono(iminopyrrolate) complexes ZrLCl4Li(OEt2)2 (2) and AlLCl2 (3) , respectively. Treatment of 3 with two equivalents of MeMgBr produced AlLMe2 (4). In addition to the spectroscopic data, all metal complexes were characterized by X-ray crystallography.

謝誌
授權書提要 i
目錄iii
圖目錄 ix
表目錄 x
壹、緒論 1
貳、實驗部分 7
一、儀器 7
二、藥品及純化 8
三、實驗步驟 12
參、結果與討論 20
一、配位基 5-tert-butyl-2-[(2,6-diisopropylphenyl) aldimino]- 20
pyrrole (HL)性質的探討 21
二、錯合物MgL2 (1)的合成及結構探討 21
三、錯合物ZrCl4LLi(OEt2)2 (2)的合成與結構探討 27
四、錯合物AlCl2L (3)的合成與結構探討 30
五、錯合物AlMe2L (4)的合成與結構探討 33
六、錯合物AlCl2L (3)和錯合物AlMe2L (4)的綜合探討 36
肆、結論 38
伍、未來展望 39
陸、參考文獻 40
柒、附錄 46
附錄1-1 5-tert-Butylpyrrole-2-carbaldehyde溶於CDCl3的1H NMR光譜 (200 MHz，RT) 46
附錄1-2 5-tert-Butylpyrrole-2-carbaldehyde溶於C6D6的1H NMR 光譜 (200 MHz，RT) 47
附錄1-3 5-tert-Butylpyrrole-2-carbaldehyde溶於CDCl3的 13C{1H } NMR光譜 (75 MHz，RT) 48
附錄1-4 5-tert-Butylpyrrole-2-carbaldehyde GC/MS 圖譜 49
附錄2-1 配位基5-tert-butyl-2-[(2,6-diisopropylphenyl)aldimino]- pyrrole (HL)溶於CDCl3的1H NMR光譜 (200 MHz，RT) 50
附錄2-2 配位基5-tert-butyl-2-[(2,6-diisopropylphenyl)aldimino]- pyrrole (HL)溶於C6D6的1H NMR光譜 (200 MHz，RT) 51
附錄2-3 配位基5-tert-butyl-2-[(2,6-diisopropylphenyl)aldimino]- pyrrole (HL)溶於CDCl3 13C{1H } NMR光譜 (75 MHz，RT) 52
附錄2-4 配位基5-tert-butyl-2-[(2,6-diisopropylphenyl)aldimino]- pyrrole (HL) GC/MS 圖譜 53
附錄2-5 配位基5-tert-butyl-2-[(2,6-diisopropylphenyl)aldimino]- pyrrole (HL) IR圖譜 54
附錄2-6 配位基5-tert-butyl-2-[(2,6-diisopropylphenyl)aldimino]- pyrrole (HL) 的元素分析 55
附錄 3-1 錯合物MgL2 (1) 溶於C6D6的1H NMR光譜(200 MHz，RT) 56
附錄 3-2 錯合物MgL2 (1)溶於C6D6的 13C{1H } NMR光譜 (75MHz，RT) 57
附錄 3-3 錯合物MgL2 (1) 的元素分析 58
附錄3-4 Crystal data and structure refinement for MgL2 (1) 59
附錄3-5 Atomic coordinates and occupancy for MgL2 (1) 62
附錄3-6 Anisotropic displacement parameters for MgL2 (1) 67
附錄3-7 Bond lengths ( Ao ) for MgL2 (1) 69
附錄3-8 Bond angles ( o ) for MgL2 (1) 72
附錄3-9 Torsion angles ( o ) for MgL2 (1) 79
附錄3-10 Non-bonded contacts out to 3.60 Ao for MgL2 (1) 90
附錄4-1 錯合物ZrCl4LLi(OEt2)2 (2) 溶於C6D6的1H NMR光譜 (200 MHz，RT) 92
附錄4-2 錯合物ZrCl4LLi(OEt2)2 (2) 溶於C6D6的 13C{1H } NMR 光譜 (125 MHz，RT) 93
附錄4-3 錯合物ZrCl4LLi(OEt2)2 (2) 溶於C6D6的 Dept 光譜 (125 MHz，RT) 94
附錄4-4 錯合物ZrCl4LLi(OEt2)2 (2) 的元素分析 95
附錄4-5 Crystal data and structure refinement for錯合物ZrCl4LLi(OEt2)2 (2) 96
附錄4-6 Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for錯合物ZrCl4LLi(OEt2)2 (2) 97
附錄4-7 Bond lengths [Å] and angles [°] for 錯合物ZrCl4LLi(OEt2)2 (2) 99
附錄4-8 Anisotropic displacement parameters (Å2x 103) for錯合物ZrCl4LLi(OEt2)2 (2) 103
附錄 4-9 Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for 錯合物ZrCl4LLi(OEt2)2 (2) 105
附錄 5-1 錯合物AlCl2L (3) 溶於C6D6的1H NMR光譜(200 MHz，RT) 107
附錄 5-2 錯合物AlCl2L (3) 溶於C6D6的 13C{1H } NMR光譜 (75MHz，RT) 108
附錄 5-3 錯合物AlCl2L (3) 溶於C6D6未接觸過空氣的1H NMR光譜(200 MHz，RT) 109
附錄 5-4 錯合物AlCl2L (3) 溶於C6D6接觸空氣24小時的1H NMR光譜(200 MHz，RT) 110
附錄 5-5 錯合物AlCl2L (3) 的元素分析 111
附錄 5-6 Crystal data and structure refinement for AlCl2L (3) 112
附錄 5-7 Atomic coordinates and occupancy for AlCl2L (3) 115
附錄 5-8 Anisotropic displacement parameters for AlCl2L (3) 118
附錄 5-9 Bond lengths ( Ao ) for AlCl2L (3) 119
附錄 5-10 Bond angles ( o ) for AlCl2L (3) 121
附錄 5-11 Torsion angles ( o ) for AlCl2L (3) 125
附錄 5-12 Non-bonded contacts out to 3.60 Ao for AlCl2L (3) 130
附錄 5-13 Least-squares planes for AlCl2L (3) 131
附錄 6-1 錯合物AlMe2L (4) 溶於C6D6的1H NMR光譜(500 MHz，RT) 132
附錄 6-2 錯合物AlMe2L (4) 溶於C6D6的13C{1H } NMR光譜 (125MHz，RT) 133
附錄 6-3 錯合物AlMe2L (4) 溶於C6D6的 Dept光譜 (125MHz，RT) 134
附錄 6-4 錯合物AlMe2L (4) 溶於C6D6在80 ℃反應72小時的1H NMR光譜(200 MHz，RT) 135
附錄 6-5 錯合物AlMe2L (4) 溶於C6D6未接觸過空氣的1H NMR光譜(200 MHz，RT) 136
附錄 6-6 錯合物AlMe2L (4) 溶於C6D6接觸空氣24小時的1H NMR光譜(200 MHz，RT) 137
附錄 6-7 錯合物AlMe2L (4) 的元素分析 138
附錄 6-8 Crystal data and structure refinement for AlMe2L (4) 139
附錄 6-9 Atomic coordinates and occupancy for AlMe2L (4) 142
附錄 6-10 Anisotropic displacement parameters for AlMe2L (4) 145
附錄 6-11 Bond lengths ( Ao ) for AlMe2L (4) 147
附錄 6-12 Bond angles ( o ) for AlMe2L (4) 149
附錄 6-13 Torsion angles ( o ) for AlMe2L (4) 152
附錄 6-14 Non-bonded contacts out to 3.60 Ao for AlMe2L (4) 154
捌、其它合成出的化合物 155
8-1. 5-tert-Butyl-pyrrol-2-yl-methanol溶於CDCl3的1H NMR光譜 (200 MHz，RT) 160
8-2. N,N-bis[2-(p-tolylsulfonyloxy)ethyl]toluene-p-sulfonamide溶於CDCl3的1H NMR光譜(200 MHz，RT)161
8-3 錯合物Ni(PPh3)4溶於toluene的31P-NMR光譜(121.5 MHz，RT) 162
8-4 錯合物Ni(PPh3)3PhCl溶於toluene的31P-NMR光譜(121.5 MHz，RT) 163
8-5-1 2,6-Dichloroiodobenzene溶於CDCl3的1H-NMR光譜 (200 MHz，RT) 164
8-5-2 2,6-Dichloroiodobenzene 的GC/MS 圖譜165
8-6 錯合物{2-[(2,6-C6H3iPr2)NCH]NC4H3}2Mg(OEt2)2 (5)的分子結構圖 166
8-7 Crystal data and structure refinement for {2-[(2,6-C6H3iPr2)NCH]NC4H3}2Mg(OEt2)2 (5) 167
8-8 Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for {2-[(2,6-C6H3iPr2)NCH]NC4H3}2Mg(OEt2)2 (5) 168
8-9 Bond lengths [Å] and angles [°] for {2-[(2,6-C6H3iPr2)NCH]NC4H3}2Mg(OEt2)2 (5) 170
8-10 Anisotropic displacement parameters (Å2x 103) for {2-[(2,6-C6H3iPr2)NCH]NC4H3}2Mg(OEt2)2 (5) 174
8-11 Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103)for{2-[(2,6-C6H3iPr2)NCH]NC4H3}2Mg(OEt2)2 (5) 176

圖目錄
圖1 形成烯類聚合反應催化劑的三種反應路徑(A、B、C) 1
圖2 含氮雙牙配位基 4
圖3 錯合物[2-(RNCH)C4H3N]2TiCl2 (R=C6H5，cyclo-C6H11) 5
圖4 本論文所使用的配位基5-tert-butyl-2-[(2,6-diisopropylphenyl)- aldimino]pyrrole (HL) 6
圖5 本論文中所有反應的流程圖 19
圖6 錯合物1(MgL2) 升溫1H核磁共振光譜(NMR)，由25 ℃→80 ℃ 23
圖7 Molecular structure of MgL2 (1) 25
圖8 Molecular structure of ZrCl4LLi(OEt2)2 (2) 29
圖9 Molecular structure of AlCl2L (3) 32
圖10 Molecular structure of AlMe2L (4) 35
圖11 錯合物4 (AlMe2L) 升溫核磁共振光譜(NMR)，由25 ℃→80 ℃ 37
表目錄
表1 本論文中錯合物1、2、3、4之晶體相關資料總整理表 26

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