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研究生： 蔡篤慰
Du Wei Tsai
論文名稱： 三配位釩金屬錯合物及其亞胺基衍生物
Three Coordinate Vanadium Complex and Its Imido Derivatives
指導教授： 蔡易州
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2005
畢業學年度： 93
語文別： 中文
中文關鍵詞： 釩 、三配位 、低配位 、亞胺 、釩氮三鍵 、重氮烷 、疊氮烷
外文關鍵詞： vanadium, three coordinate, low coordinate, imido, VN triple bond, diazoalkane, organoazide
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    • 我們將VCl3(thf)3分别和兩個我們自行設計的配基N,N’-cyclohexyl –(2,6-diisopropylphenyl)amino Lithium及N,N’-cyclohexyl –(2,4,6-trimethylphenyl)amino Lithium混合，合成出兩個新的偽三配位金屬錯合物(masked three coordinate complex) Complex 1 [VCl(THF)(N(Cy)dipp)2]及Complex 2 [VCl(THF) (N(Cy)dipp)2]。
    以Complex 1為金屬中心分別和N2-C(H)TMS及N3-R (R=Mes,TMS)反應，可得到三個organoimido vanadium complex 產物Complex 3 [(TMS-C(H)N2)VCl(THF)(N(Cy)dipp)2]、Complex 4 [(Mes-N3)VCl(THF) (N(Cy)dipp)2] 及Complex 5 [(TMS-N)VCl(THF) (N(Cy)dipp)2]並分別推測其反應機制。將用nBuLi去質子化的TMSC(H)N2分別和Complex 1反應可得到不預期的Complex 5及具有LiCN產生證據的Complex 6 [V(N(Cy)dipp)2 (CN)2Li(OEt)2]2，證明了反應可能的途徑。
    以Complex 1為金屬中心和NaN3反應，可得一個nitrido vanadium complex產物Complex 7 [V(N(Cy)dipp)2(μ-Cl)(μ-N)Na (OEt2)2]，並且將Complex 7分別和pivaloyl chloride及benzoyl chloride反應，可以得到兩個相似的結果Complex 8 [VCl(N(Cy)dipp)2(N-C(O)tBu)2]和Complex 9 [VCl(N(Cy)dipp)2 (N-C(O)Ph)2]。

    We have developed two new amino ligands [N,N’-cyclohexyl –(2,6-diisopropylphenyl) amino Lithium] and [N,N’-cyclohexyl –(2,4,6-trimethylphenyl) amino Lithium] reacting with VCl3(thf)3 to get two masked three coordinate complex: Complex 1 [VCl(THF)(N(Cy)dipp)2] and Complex 2 [VCl (THF)(N(Cy)dipp)2].To this bulkyl Complex 1,treat with N2C(H)TMS or N3R (R=Mes,TMS),we can get three organo imido vanadium complex product Complex 3 [(TMS-C(H)N2)VCl(THF)(N(Cy) dipp)2], Complex 4 [(Mes-N3)VCl(THF)(N(Cy)dipp)2] ,and Complex 5 [(TMS-N)VCl(THF)(N(Cy)dipp)2].We also treat a n-Butyl lithium deprotonating trimethylsilyldiazomethane with Complex 1 to get an unexpected product Complex 5 which lose a lithium cyanide and its side product Complex 6 [V(N(Cy)dipp)2 (CN)2Li(OEt)2]2 proving the formation of LiCN. So we can suppose the possible reaction way.
    In the other way, Complex 1 react with NaN3 affords a nitrido vanadium complex Complex 7 [V(N(Cy)dipp)2(μ-Cl)(μ-N) Na(OEt2)2]. We can get a similar result, Complex 8 [VCl(N(Cy) dipp)2(N-C(O)tBu)2] and Complex 9 [VCl(N(Cy)dipp)2(N-C(O)Ph)2] if we treat Complex 7 with pivaloyl chloride or benzoyl chloride.

    目錄 1.前言……………………………………………………………………1 1.1 低配位金屬錯合物背景……………………………………………1 1.2 organo imido metal complex of transition metal…………5 1.3 重氮烷類在配位化學上的背景……………………………………8 1.4 nitrido metal complex……………………………………………9 2. 實驗…………………………………………………………………13 2.1 一般方法 …………………………………………………………13 2.1-1 實驗過程 ………………………………………………………13 2.1-2 光譜儀器………………………………………………………13 2.1-3 實驗溶劑………………………………………………………13 2.1-4 使用藥品………………………………………………………14 2.1-5 縮寫表…………………………………………………………15 2.2 實驗步驟…………………………………………………………16 2.2-1 Ligand Part……………………………………………………16 2.2-2 Complex Part…………………………………………………23 2.3 晶體結構…………………………………………………………35 3.結構解析……………………………………………………………61 3.1 Complex 1-2………………………………………………………61 3.2 Complex 3-5………………………………………………………43 3.3 Complex 6…………………………………………………………44 3.4 Complex 7…………………………………………………………45 3.5 Complex 8-9………………………………………………………45 4. 結果討論…………………………………………………………70 4.1 organo imido complex……………………………………………70 4.2 nitrido complex…………………………………………………75 5. 結論…………………………………………………………………77 參考文獻………………………………………………………………78附錄A 晶體鍵長鍵角總表……………………………………………… 附錄B 光譜資料………………………………………………………… 圖表目錄 Fig.1……………………………………………………………………2 Fig.2……………………………………………………………………3 Fig.3……………………………………………………………………4 Fig.4……………………………………………………………………5 Fig.5……………………………………………………………………6 Fig.6……………………………………………………………………7 Fig.7……………………………………………………………………7 Fig.8……………………………………………………………………9 Fig.9……………………………………………………………………10 Fig.10…………………………………………………………………12 Fig.11…………………………………………………………………70 Fig.12…………………………………………………………………71 Fig.13…………………………………………………………………72 Fig.14…………………………………………………………………72 Fig.15…………………………………………………………………73 Fig.16…………………………………………………………………75 Fig.17…………………………………………………………………76

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