中文摘要
章節一
我們合成出一系列苯胺膦亞胺雙牙配位基，與正丁基鋰反應合成出一系列理金屬錯合物，並探討其在膦核磁共振光譜中的現象。再利用此系列配位基與鋅烷基錯合物進行反應，而得到一系列苯胺膦亞胺化鋅烷基錯合物，並透過多種核種的核磁共振光譜以及 X-ray來鑑定其結構。除此之外我們使用苯胺膦亞胺雙牙配位基以及苯胺膦雙牙配位基與醋酸鋅進行反應，得到兩種截然不同的結果。最後我們以我們合成出的苯胺膦亞胺化鋅烷基錯合物作為催化劑，對於環內酯進行開環聚合的反應。
章節二
我們利用實驗室所合成出的苯胺膦化鎳錯合物，對於滷化苯或是滷化烷與格林那試劑的偶合進行催化，除此之外，也對於苯胺膦化鎳錯合物可對苯進行碳氫鍵活化的反應，進行動力學探討，以利於我們對於此反應的機制，做出更正確的推斷

英文摘要
Chapter 1
A new chelating N,N ligand family incorporating an anilido-phosphinimine donor set has been designed. The ligand1-(NHAr)-2-(PPh2=NAr’)C6H4(iPr[NN]DippH: Ar = 2,6-iPr2-C6H3, Ar’ = 2,6-iPr2-C6H3; iPr [NN]MesH: Ar = 2,6-iPr2-C6H3, Ar’ = 2, 4, 6-Me3C6H2; Me[NN]MesH: 2,6-Me2-C6H3, Ar’ = 2, 4, 6-Me3C6H2) were synthesized via a route of reacting amido phosphine ligands with aryl azides. We observed different behaviors of adding n-BuLi in different solvents. In 31P NMR, we found the changed of chemical shift upon the different Ar’ substituents. When substituent on Nphosphinimine was Dipp, there are larger chemical shift change.
Addition of [NN]H to ZnMe2 or ZnEt2 in toluene or Et2O at -35oC generated the monomeric, three-coodinate [NN]ZnR (R = Me, Et)(schem 1), while the metathesis reaction of Zn(OAc)2 with iPr[NN]DippLi(Et2O) in THF at -35oC produced iPr[NN]DippZnOAc. But in the same condition, we made the iPr[NP] iPrLi(DME) produced homoleptic {iPr[NP] iPr}2Zn. All of the complexes were characterized by multinuclear NMR spectroscopy or X-ray crystallography.
We used [NN]ZnR catalyzed ring-opening polymerization of ε-Caprolactone
. The results of catalysis had good yields in 90 to 100% and narrow PDI around 1.5. But they are not a living polymerization catalysis.
Chapter 2
We use {[NP]NiCl}2 catalyzed Kumada reactions of alkyl halide or aryl halide with Grignard reagent. In the result, Used {iPr[NP]iPr}2NiCl catalyzed aryl halide with Grignard reagent is better than other {[NP]}2NiCl, but not good catalyzed alkyl halide with Grignard reagent.
We do kinetic studies of benzene C-H bond activation by nickel complexes of amido phosphine ligand. By the result, We can defind the benzene C-H bond activation was association rection.

目錄
目錄Chapter 1 Zinc Complexes of Chelating Amido Ligands and Their catalytic
Ring-Opening Polymerization of ε-Caprolactone
章節一 胺基膦化物鋅錯合物及催化環內酯開環聚合反應................................................1
壹. 緒論......................................................................................................................................1
貳. 結果與討論..........................................................................................................................4
1. 苯胺膦亞胺雙牙配位基的合成及結構探討................................................................4
2. 苯胺膦亞胺化鋰錯合物的合成....................................................................................6
3. [NN]ZnR(R = Et, Me)的合成及結構探討....................................................................9
4. [NN]ZnR與醇類的反應測試.....................................................................................17
5. iPr[NN]DippZnOAc的合成及結構探討........................................................................19
6. { iPr[NP]iPr}2Zn的合成及結構探討.............................................................................21
7. 利用[NN]ZnR以及Me[NP]iPrZnR催化環內酯開環聚合反應..................................26
参. 結論...................................................................................................................................32
肆.未來與展望.........................................................................................................................33
伍.實驗部份.............................................................................................................................34
一. 一般程序.....................................................................................................................34
二. 儀器.............................................................................................................................34
三. 實驗步驟.....................................................................................................................35
1. 合成Me[NN]MesH (TLT 2-140)............................................................................35
2. 合成iPr[NN]DippLi(Et2O)(TLT 2-154)...................................................................36
3. 合成Me[NN]MesLi(Et2O) (TLT 2-150).................................................................37
4. 合成iPr[NN]DippZnMe (TLT 2-204)....................................................................38
5. 合成iPr[NN]DippZnEt (TLT 2-168)......................................................................38
6. 合成 iPr[NN]MesZnMe (TLT 3-209).....................................................................39
7. 合成 iPr[NN]MesZnEt (TLT 3-200).......................................................................40
8. 合成Me[NN]MesZnMe (TLT 3-175)..................................................................... 41
9. 合成Me[NN]MesZnEt(TLT 3-175)........................................................................42
10. 合成 iPr[NN]DippZnOAc (TLT 3-60)....................................................................43
11. 合成[iPr[NP]iPr]2Zn (TLT 3-16)............................................................................44
12.ε-Caprolactone的開環聚合反應........................................................................45
陸.參考文獻.............................................................................................................................45
Chapter 2 Amido Phosphine Complexes of Nickel: Catalytic Kumada Reactions and Kinetic
Studies of Benzene C-H Bond Activation
章節 二 胺基膦化物鎳金屬錯合物之催化應用.............................................................48
壹. 緒論...................................................................................................................................48
貳. 結果與討論.......................................................................................................................50
(1) Kumada coupluing
1.Kumada coupluing條件篩選....................................................................................50
2.Kumada coupluing的反應測試................................................................................54
(2) Kinetic Studies of Benzene C-H Bond Activation
1.鎳錯合物對於不同溫度的動力學實驗....................................................................57
2.鎳錯合物對於額外添加路易士鹼的動力學實驗....................................................61
参.結論.....................................................................................................................................67
肆.未來與展望.........................................................................................................................68
伍. 實驗部份...........................................................................................................................68
一. 一般程序.....................................................................................................................68
二. 儀器.............................................................................................................................68
三. 實驗步驟.....................................................................................................................66
1. Kumada coupling..................................................................................................69
2. 鎳錯合物對於不同溫度的動力學實驗..............................................................69
3. 鎳錯合物對於額外添加路易士鹼的動力學實驗..............................................69
陸.參考文獻.............................................................................................................................70
附錄..........................................................................................................................................68
一. 其他化合物的合成鑑定.............................................................................................72
二. 環內酯開環聚合的線性關係圖.................................................................................73
三. 鎳錯合物對於苯在不同溫度進行碳氫鍵活化積分值、積分值取倒數為縱座標
，時間為橫座標圖.....................................................................................................75
四. Crystallographic Data.................................................................................................79
圖目錄
章節一
圖1.文獻中BDI配位基骨架參與反應...........................................................................2
圖2. 雙牙配位基示圖......................................................................................................3
圖 3. 利用氨基膦化物與疊氮反應合成氨基膦亞胺配位基.........................................4
圖 4. Me[NN]MesH晶體結構圖.........................................................................................6
圖 5. iPr[NN]DippZnMe以及Me[NN]MesZnMe晶體結構圖.............................................14
圖 6. iPr[NN]MesZnMe晶體結構圖.................................................................................15
圖 7. iPr[NN]DippZnEt以及iPr[NN]MesZnEt晶體結構....................................................16
圖 8. Me[NN]MesZnEt晶體結構......................................................................................17
圖 9. 鋅烷基與醇進行酸鹼中和反應...........................................................................18
圖 10. 配位基與鋅金屬六元環的比較.........................................................................19
圖 11. 推測{iPr[NN]DippZnOAc}2的結構......................................................................20
圖 12. iPr[NN]DippZnOAc晶體結構圖............................................................................21
圖 13. { iPr[NP]iPr}2Zn晶體結構圖.................................................................................23
圖 14. 甲基坐落於苯環上.............................................................................................27
圖 15.ε-Caprolactone開環聚合物氫的核磁共振光譜圖(A)文獻光譜(B)本文實驗光譜(entry 38 in table 7)............................................................................................28
圖 16. 以Me[NN]MesZnEt作為催化劑的線性關係圖..................................................29
圖 17. 催化劑iPr[NN]DippZnEt(0.047 M)與一倍單體的1H NMR追蹤光譜(300 Hz, C6D6) (A)ε-caprolactone (B) iPr[NN]DippZnEt (C)ε-caprolactone + iPr[NN]DippZnEt at RT(5 min) (D)ε-caprolactone + iPr[NN]DippZnEt at 80oC(6 min).....................................................................................................................32
章節二
圖 1 cross coupling .........................................................................................................49
圖 2 (A) Terao and Kambe proposed catalytic cycle for Kumada coupling (B)Proposed catalytic cycle for Kumada coupling by amido phosphine Nickel complexes...........53
圖 3鎳錯合物對於苯在不同溫度進行碳氫鍵活化.....................................................59
圖 4推測鎳錯合物對於苯進行碳氫鍵活化的反應機制.............................................62
圖 5鎳錯合物對於苯在不同溫度進行碳氫鍵活化的反應速率作Eyring plot..........62
圖 6 鎳錯合物對於苯在進行碳氫鍵活化中額外添加路易士鹼................................64
圖 7 鎳錯合物對於苯在進行碳氫鍵活化中額外添加路易士鹼對於反應常數取自然
對數為縱座標，對於添加倍數取自然對數為橫坐標作圖................................66
表格目錄
章節一
表 1. 31P NMR Spectroscopic Data of Ligands................................................................7
表2. Selected NMR Spectroscopic Data of [NN]Li(solvent)n.........................................8
表3. Selected NMR Spectroscopic Data of [NN]ZnR....................................................12
表4 [NN]ZnMe鍵長(Å)以及鍵角(deg)比較................................................................13
表 5 [NN]ZnEt鍵長(Å)以及鍵角(deg)比較.................................................................15
表6 [NP]2Zn Dihedral Angle和Devaiation.....................................................................24
表7 31P NMR Spectroscopic Data of amido phosphine of Zinc.....................................26
表8 環內酯開環聚合反應............................................................................................30
章節二
表1 Effects of solvents, temperatures and catalysts on catalytic Kumada reactions of
n-BuMgCl with bromobenzene…………………………………………………....52
表2 Catalytic Kumada Reactions of Grignard Reagents with Aryl Halides....................55
表3 Catalytic Kumada Reactions of Grignard Reagents with Alkyl Halides..................56
表4 鎳錯合物對於苯在不同溫度進行碳氫鍵活化的反應速率...............................61
表5 鎳錯合物對於苯在進行碳氫鍵活化的ΔH≠, ΔS≠..................................................63
表6 鎳錯合物對於苯在進行碳氫鍵活化中額外添加路易士鹼的反應常數..............66
式目錄
章節一
式1 合成Me[NN]MesH......................................................................................................5
式2 合成[NN]Li(solvent)n...............................................................................................8
式3 合成[NN] ZnR(R = Et, Me).....................................................................................10
式4 合成iPr[NN]DippiPrZnOAc..........................................................................................19
式5 合成{ iPr[NP]iPr}2Zn...................................................................................................22
章節二
式1 鎳錯合物對於苯進行碳氫鍵活化.........................................................................50

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