第一部分: 膦胺配位基鎳二價錯合物的合成與反應性探討
我們合成出[Me-NP-iPr]Ni(CH2SiMe3)(L)(L=2,6-lutidine)與實驗室成員所合成的[Me-NP-iPr]Ni(CH2SiMe3)(L)(L= pyridine, 2,4lutidine, PMe3)做為比較，探討改變Lewis base後該錯合物對benzene進行碳氫鍵活化的速率。同時也利用PhMgCl試劑與[Me-NP-iPr]Ni(2,6-lutidine)(Cl)合成出[Me-NP-iPr]Ni(2,6-lutidine)(Ph)證實了CH2SiMe3取代的錯合物活化benzene的碳氫鍵後得到的產物[Me-NP-iPr]Ni(R)(L)(L=2,6-lutidine; R= CH2SiMe3, Ph)錯合物的溶液態結構也利用NMR進行鑑定，同時也得到了[Me-NP-iPr]Ni(R)(L)(L=2,6-lutidine; R= Cl, Ph)的晶體進行固態結構的分析。[Me-NP-iPr]Ni(CH2SiMe3)(2,6-lutidine)對benzene進行碳氫鍵活化的半生期、反應級數與速率常數也經由動力學實驗得到相對應的資料。

第二部分: 膦胺配位基鋯四價錯合物的合成與反應性測試
使用實驗室成員所合成出的[iPr-PNP]Zr(=CHSiMe3)(Cl)作為起始物加入MgClCH2SiMe3試劑，合成出[iPr-PNP]Zr(=CHSiMe3)(CH2SiMe3)，溶液態結構與固態結構接經由NMR光譜與X-Ray繞射分析所鑑定。欲利用立體障礙的效應進行α-氫離去反應得到[iPr-PNP]Zr(≡CHSiMe3)(L)(L= solvent)，目前並未得到理想的結果。改變合成途徑為使用[PhNHMe2]+[B(C6F5)4]-，企圖氧化CH2SiMe3取代基得到{[iPr-PNP]Zr(=CHSiMe3)+}{B}-離子化合物，結果得到{[iPr-PNP]Zr(CH2SiMe3)2}+{B(C6F5)4}-，溶液態結構與固態結構接經由NMR光譜與X-Ray繞射分析所鍵定。

First Part: Syntheses of Diarylamidophosphino Nickel(II) Complexes and reactivity study
We have synthesized [Me-NP-iPr]Ni(CH2SiMe3)(L)(L=2,6-lutidine). In order to compare with [Me-NP-iPr]Ni(CH2SiMe3)(L)(L= pyridine, 2,4lutidine, PMe3), benzene C-H activation reaction experiment were carried out and rate constant were determined by kinetic study. We also synthesized [Me-NP-iPr]Ni(Ph)(2,6-lutidine) to prove the benzene C-H activation product by the trimethylsilylmethyl substituted Ni complex. Solution structure of [Me-NP-iPr]Ni(R)(L)(L=2,6-lutidine; R= CH2SiMe3, Ph) and Solid structure of [Me-NP-iPr]Ni(R)(L)(L=2,6-lutidine; R= Cl, Ph) were characterized by NMR spectroscopy and X-Ray diffraction.

Second Part: Syntheses of Diarylamidophosphino Zirconium(IV) Complexes and reactivity test
Use [iPr-PNP]Zr(=CHSiMe3)(Cl) as starting material to react with PhMgCl yield [iPr-PNP]Zr(=CHSiMe3)(CH2SiMe3). Solution and Solid structure of [iPr-PNP]Zr(=CHSiMe3)(CH2SiMe3) were characterized by NMR spectroscopy and X-Ray diffraction. Experiments for inducing intramolecular α-H abstruction to afford [iPr-PNP]Zr(≡CHSiMe3)(L)(L= solvent) were unsuccessful. Attempt to oxidize trimethylsilylmethyl substitution with [PhNHMe2]+[B(C6F5)4]- resulting protonated product {[iPr-PNP]Zr(CH2SiMe3)2}+{B(C6F5)4}-, solution and solid structure were also characterized.

目錄
Synthesis of Ni Complexes Containing Diarylamido Phosphine Ligand and Reactivity Study 1
1.1序論 1
1.2 結果與討論 6
1.2.1 合成[Me-NP-iPr]Ni(L)(Cl)、[Me-NP-iPr]Ni(L)(CH2SiMe3)及[Me-NP-iPr]Ni(L)(Ph) (L=2,6-lutidine) 6
1.2.2 [Me-NP-iPr]Ni(2,6-lutidine)(CH2SiMe3)對benzene進行C-H鍵活化動力學實驗 15
1.3 結論 17
1.4 未來展望 17
1.5 實驗部分 18
1.5.1一般程序 18
1.5.2儀器 18
1.5.2合成[MeNPiPr]Ni(2,6-lutidine)(Cl) (cwl1-135, cwl2-149) 19
1.5.3合成[MeNPiPr]Ni(2,6-lutidine)(CH2SiMe3) (cwl1-172) 19
1.5.4合成[MeNPiPr]Ni(2,6-lutidine)(Ph) (cwl2-211) 20
1.5.5 [MeNPiPr]Ni(2,6-lutidine)(CH2SiMe3)對benzene進行C-H鍵活化動力學實驗(cwl1-220) 21
2. Synthesis of Zr Complexes Containing Diarylamido Phosphine Ligand and Reactivity Test 22
2.1序論 22
2.2結果與討論 26
2.2.1合成[iPr-PNP]Zr(=CHSiMe3)(CH2SiMe3) 26
2.2.1企圖合成[iPr-PNP]Zr(≡CSiMe3)(L) 31
2.2.2合成{[iPr-PNP]Zr(CH2SiMe3)2}+{B(C6F5)4}- 33
2.3結論 36
2.4未來展望 37
2.5實驗部分 37
2.5.1合成[iPr-PNP]Zr(CH2SiMe3)(=CHSiMe3) (cwl2-50) 37
2.5.2合成{[iPr-PNP]Zr(CH2SiMe3)2}+{B(C6F5)4}- (cwl2-202) 39
3. 參考文獻 40
4.附錄 45
4.1嘗試[iPr-PNP]ZrH3、[iPr-PNP]Zr(=CHSiMe3)(R)(R= H, OTf) 45
4.1.1嘗試合成[iPr-PNP]ZrH3 (cwl2-162) 45
4.1.2嘗試合成[iPr-PNP]Zr(=CHSiMe3)(H) (cwl2-228) 45
4.1.3嘗試合成[iPr-PNP]Zr(=CHSiMe3)( OTf) (cwl2-229) 46
4.2 嘗試合成[iPr-PNP]Hf(=CHSiMe3)(Cl) (cwl2-222) 46
4.3 [iPr-PNP]ZrCl3的還原反應 (cwl1-259) 46
4.4 合成KC8 47
4.5 X-Ray 晶體資料 48

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