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| 研究生： |
黃昱翔 Huang, Yu-Siang |
|---|---|
| 論文名稱： |
雙氮基脒與β-二酮亞胺雙鉻錯合物對炔、腈與胺硼烷類之反應歧性 Reactivity Diversity of Dichromium Amidinates and β-Diketiminates toward Alkyne, Nitrile and Amine-Borane |
| 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： | 66 |
| 中文關鍵詞： | 雙氮基脒 、二酮亞胺 、雙鉻錯合物 、反應歧性 |
| 外文關鍵詞： | Amidinates, Diketiminates, Dichromium, Diversity |
| 相關次數： | 點閱：2 下載：0 |
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本實驗室以雙氮基脒為配基合成出低配位低價數之雙鉻金屬五重鍵錯合物Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (1)。將錯合物1與一當量炔類分子如三甲基矽乙炔、叔丁基乙炔與苯乙炔進行反應，則分別得到(μ-κ2-(CH3)3SiCCH)Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (2)、(μ-κ2-(CH3)3CCCH)Cr2[μ
-κ2-HC(N-2,6-iPr2C6H3)2]2 (3)及(μ-κ2-(C6H5)CCH)Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (4)等三轉軸雙鉻四重鍵錯合物；另外僅在錯合物1與三甲基矽乙炔的反應中，我們發現三當量的三甲基矽乙炔與錯合物1反應後能夠形成[μ-η6:η6-(1,3,5-(SiMe3)3C6H3)]Cr2[κ2-HC(N-2,6-iPr2C6H3)2]2 (5)反三明治結構的雙鉻錯合物，且我們發現將錯合物5溶於四氫呋喃中或是與2,4,6-三甲基苯甲腈反應，會再次形成雙鉻五重鍵錯合物1。若將錯合物1或5與腈類分子如苯甲腈、2-甲基苯甲腈、4-甲基苯甲腈及3-甲基-4-甲氧基苯甲腈反應，皆可得到相同結構的產物，分別為(μ-κ1C:κ2N-PhCN)2(κ1-PhCN)2Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (6)、(μ-κ1C:κ2N-o-tolylCN)2(κ1-o-tolylCN)2Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (7)、(μ-κ1C:κ2N-p-tolyl-CN)2(κ1-p-tolylCN)2Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (8)及(μ-κ1C:κ2N-2-methoxy-m-tolylCN)2(κ1-2-methoxy-m-tolylCN)2Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (9)。我們也嘗試錯合物5與三甲基矽乙炔、1-戊炔與苯乙炔的反應，研究其催化三聚合環化反應的進行。最後，我們也嘗試將錯合物1與吡啶硼烷反應，發現其進行了碳-氫鍵活化反應，並得到Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2(μ-H)(μ-κ2-C5H4BH3) (10)。
另外我們以β-二酮亞胺配基合成出反三明治雙鉻錯合物(μ-η6:η6-C7H8)[Cr(Nacnac)]2 (11) (Nacnac = HC((CMe)NC6H3-iPr2)2)並與腈類分子進行反應，當錯合物11與2-甲基苯甲腈反應，得到Cr(Nacnac)(o-tolylCN)[NH(3-(o-tolyl)isoquinoline)] (12)；當11與2,4,6-三甲基苯甲腈反應，則得到Cr(Nacnac)[κ2-HN(C-2,4,6-Me3C6H2)2NH] (13)。兩個反應皆有碳-碳鍵偶合的發生。
最後我們嘗試了以鉻單核錯合物Cr[κ2-HC(N-2,6-iPr2C6H3)2]2 (14)與二氯亞鈷反應，得到了異核雙核金屬錯合物Co[κ1-HC(N-2,6-iPr2C6H3)2][μ-κ2-HC(N-2,6
-iPr2C6H3)2]Cr[κ2-HC(N-2,6-iPr2C6H3)2] (15)。
Our group have reported the synthesis of low-coordinate and low-valent quintuply-bonded dichromium complex Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (1). Treatment of 1 with alkynes afforded a family of alkyne-complexed compounds (μ-κ2-(CH3)3SiCCH)Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (2), (μ-κ2-(CH3)3CCCH)Cr2[μ-
κ2-HC(N-2,6-iPr2C6H3)2]2 (3) and (μ-κ2-(C6H5)CCH)Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (4), which all feature a Cr-Cr quadruple bond. When treatment of 1 with three equivalents of ethynyltrimethylsilane, we obtain an inverted-sandwich compound [μ-η6:η6-(1,3,5-(SiMe3)3C6H3)]Cr2[κ2-HC(N-2,6-iPr2C6H3)2]2 (5). This result is only observed in the reaction with 1 and ethynyltrimethylsilane. Surprisingly, after 5 dissolved in tetrahydrofuran or reacts with 2,4,6-trimethylbenzonitrile, 5 turns back to 1. Treatment of 1 or 5 with a series of benzonitrile, they show identical reacitivity and afforded compounds with same structure (μ-κ1C:κ2N-PhCN)2(κ1-PhCN)2Cr2[μ-κ2-HC(
-N-2,6-iPr2C6H3)2]2 (6), (μ-κ1C:κ2N-o-tolylCN)2(κ1-o-tolylCN)2Cr2[μ-κ2-HC(N-2,6-iP
-r2C6H3)2]2 (7), (μ-κ1C:κ2N-p-tolyl-CN)2(κ1-p-tolylCN)2Cr2[μ-κ2-HC(N-2,6-iPr2C6H3
-)2]2 (8) and (μ-κ1C:κ2N-2-methoxy-m-tolylCN)2(κ1-2-methoxy-m-tolylCN)2Cr2[μ-κ2-
-HC(N-2,6-iPr2C6H3)2]2 (9). 5 show excellent yield and regioselectivity in the cyclotrimerization with alkynes. Last, treatment of 1 with pyridine-borane generated Cr2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2(μ-H)(μ-κ2-C5H4BH3) (10) during C-H bond activation.
(μ-η6:η6-C7H8)[Cr(Nacnac)]2 (11) (Nacnac = HC((CMe)NC6H3-iPr2)2), an inverted-sandwich dichromium compelex is prepared. Treatment 11 with 2-methylbenzonitrile and 2,4,6-trimethylbenzonitrile afforded Cr(Nacnac)(o-tolylCN)
-[NH(3-(o-tolyl)isoquinoline)] (12) and Cr(Nacnac)[κ2-HN(C-2,4,6-Me3C6H2)2NH] (13). Both reactions involve C-C coupling.
Treatment mononuclear chromium complex Cr[κ2-HC(N-2,6-iPr2C6H3)2]2 (14) with CoCl¬2 obtained hetero-dinuclear complex Co[κ1-HC(N-2,6-iPr2C6H3)2][μ-κ2-HC(
-N-2,6-iPr2C6H3)2]Cr[κ2-HC(N-2,6-iPr2C6H3)2] (15).
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