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| 研究生： |
鄔思廷 Wu, Szu-Ting |
|---|---|
| 論文名稱： |
追求含雙氮基脒和α-二亞胺配基之雙鎢金屬五重鍵錯合物 On the Pursuit of the Quintuply Bonded Ditungsten Complexes with Amidinato and α-Diimino Ligands |
| 指導教授： |
蔡易州
Tsai, Yi-Chou |
| 口試委員: |
莊士卿
Chuang, Shih-Ching 劉學儒 Liu, Hsueh-Ju |
| 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： | 2017 |
| 畢業學年度： | 105 |
| 語文別： | 中文 |
| 論文頁數： | 74 |
| 中文關鍵詞： | 雙鎢金屬多重鍵 、四氫呋喃開環 、卡拜 、碳氫鍵活化 |
| 外文關鍵詞： | Ditungsten, carbyne |
| 相關次數： | 點閱：3 下載：0 |
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我們成功透過錫球進行鎢金屬錯合物WCl4(DME)的還原反應，製備出高純度鎢(III)金屬錯合物W2Cl6(DME)2 (2)，改善文獻製程。利用3當量去質子化的雙氮基脒[Li(THF)2][PhC(N-2,6-iPr2C6H3)2] (L1)與錯合物2進行反應，可得順磁性雙鎢金屬錯合物W2(μ-Cl)Cl2[μ-κ2-PhC(N-2,6-iPr2C6H3)2]2 (3)。將錯合物3以鉀石墨進行一個電子的還原反應，可以分離出逆磁性雙鎢金屬錯合物W2(μ-Cl)[Cl2Li(OEt2)][μ-κ2-PhC(N-2,6-iPr2C6H3)2]2 (4)。進一步將錯合物4以鉀石墨進行兩個電子的還原反應，得到逆磁性雙鎢金屬錯合物W2(μ-H)2[μ-κ2-PhC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(κ1-CH2)CH3-C6H3)]2 (5)，高活性的鎢金屬中心與雙氮基脒上的異丙基發生了有趣的碳-氫鍵的氧化加成反應；我們也發現錯合物4在有機溶劑中會發生自身氧化還原反應，生成錯合物3和5。
以α-二亞胺配基2,6-iPr2C6H3-DAB (2,6-iPr2C6H3-DAB = 1,4-bis-(2,6-iPr2C6H3)-1,4-diaza-1,3-butadiene) (L2)與1當量WCl4(DME)反應，可以得到單核鎢金屬錯合物WCl4(κ2-2,6-iPr2C6H3-DAB) (6)。以1.5當量的鈉汞齊還原錯合物6，可以分離出雙鎢金屬錯合物W2(μ-Cl)3Cl2(κ2-2,6-iPr2C6H3-DAB)2 (7)，但錯合物7無法再被進一步還原。
將雙鎢金屬錯合物W2(μ-H)2(THF)[μ-κ2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(κ1-CH2)CH3-C6H3)]2 (1c)與3當量的氯仿於四氫呋喃下進行反應，意外分離出逆磁性雙鎢金屬錯合物W2(μ-Cl)Cl2[μ-(κ1;κ2)-C(CH2)3O][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (9)；四氫呋喃分子進行開環反應，並配位在雙鎢金屬上，具有一卡拜(carbyne)橋接雙鎢金屬中心。
This thesis shows the synthesis of ditungsten complexes by the use of amidinate and α-diamino ligands. We could improve the yields of tungsten precursor, reduction of WCl4(DME) with Sn granules afforded pure W2Cl6(DME) (2). Treatment of 2 with 3 equiv. of [Li(THF)2][PhC(N-2,6-iPr2C6H3)2] (L1) produced a mix-valent ditungsten complex W2(μ-Cl)Cl2[μ-κ2-PhC(N-2,6-iPr2C6H3)2]2 (3). Upon reducing 3 with 1 equiv. of KC8 gave a quadruply bonded ditungsten species W2(μ-Cl)[Cl2Li(OEt2)][μ-κ2-PhC(N-2,6-iPr2C6H3)2]2 (4). Furthermore, complex 4 underwent 2 electron reduction with KC8 and produced a C-H bond activated ditungsten complex W2(μ-H)2[μ-κ2-PhC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(κ1-CH2)CH3-C6H3)]2 (5). Surprisingly, complex 4 converted into 3 and 5 in hydrocarbon solvents via a disproportionation reaction.
Reaction of WCl4(DME) with 2,6-iPr2C6H3-DAB (2,6-iPr2C6H3-DAB = 1,4-bis-(2,6-iPr2C6H3)-1,4-diaza-1,3-butadiene) (L2) afforded a mononuclear WCl4(κ2-2,6-iPr2C6H3-DAB) (6). Upon reduction of 6 with 1.5 equiv. of Na/Hg produced a ditungsten W2(μ-Cl)3Cl2(κ2-2,6-iPr2C6H3-DAB)2 (7), which is hard to be reduced further. Treatment of W2(μ-H)2(THF)[μ-κ2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(κ1-CH2)CH3-C6H3)]2 (1c) with 3 equiv. of CHCl3 in THF gave a THF ring opened ditungsten species W2(μ-Cl)Cl2[μ-(κ1;κ2)-C(CH2)3O][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (9), which features a bridging carbyne ligand moiety.
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