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| 研究生： |
馮雅瑄 Feng, Ya-Hsuan |
|---|---|
| 論文名稱： |
雙鉬金屬五重鍵錯合物與含氮雜苯、腈類和白磷的反應性研究 Reaction Studies of the Mo-Mo Quintuple Bond with Aza-Containing Arenes, Nitriles and White Phosphorus |
| 指導教授： |
蔡易州
Tsai, Yi-Chou |
| 口試委員: |
劉學儒
Liu, Hsueh-Ju 尤禎祥 Yu, Jen-Shiang |
| 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： | 2018 |
| 畢業學年度： | 106 |
| 語文別： | 中文 |
| 論文頁數： | 99 |
| 中文關鍵詞： | 雙鉬金屬五重鍵 、芳香烴錯合化 、腈類 、活化白磷 |
| 外文關鍵詞： | Mo-Mo Quintuple Bonded, arene complexation, nitrile, P4 Activation |
| 相關次數： | 點閱：2 下載：0 |
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本實驗室以雙氮基脒[LiHC(N-2,6-iPr2C6H3)2]為配位基合成出第一個雙鉬金屬五重鍵錯合物Mo2[μ-2-HC(N-2,6-iPr2C6H3)2]2 (1)，本論文主要探討錯合物1與含氮雜苯、腈類與白磷的反應性。
錯合物1與2,2'-聯吡啶反應，可以得到錯合物Mo2(μ-η2-1,2:η2-4,5-C10H8N2)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (2)及(η2-C10H8N2)2Mo2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (3)，錯合物2中的2,2'-聯吡啶反應以面配位於雙金屬上，不同於錯合物3藉由常見方式將氮上的孤電子螯合在金屬上。1與異喹啉和喹喔啉反應同樣可以得到含氮雜苯以面配位於金屬上的錯合物Mo2(μ-η2-1,2:κ1-4-R)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (R = C9H7N (4), C8H6N2(5))；但是與喹啉反應時，則會經由八號位的碳-氫鍵被活化而氧化加成至鉬-鉬形成錯合物Mo2(H)(μ-κ2-C9H7N)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (6)。
錯合物1分別與氰基苯甲酸甲酯、對甲氧基苯甲腈及1,8-萘二甲腈反應時，會進行[2+2+2]環化加成反應，得到錯合物Mo2[μ-κ2-NC(R)C(R)N][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (R = C6H4CO2CH3 (7), C6H4OCH3 (8), C5H3 (9))；然而與對二甲基胺苯甲腈反應卻得到碳-氫鍵活化的產物[κ1-NCC6H4N(CH3)2][μ-κ1-NC(H)C6H4NH(CH3)2]Mo2[μ-κ2-HC(N-2,6-iPr2C6H3)(N-2-iPr-6-CH(κ1-CH2)CH3-C6H3][μ-κ2-HC(N-2,6-iPr2C6H3)2] (10) 。與具有雙腈基的化合物反應時，1,8-萘二甲會進行[2+2+2]環化加成反應得到錯合物9；鄰苯二甲腈會與錯合物1進行二次[2+2+2]環化反應後，形成八員環的錯合物(C16H8)(μ-κ2-N2)2{Mo2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2}2 (11)；聯苯甲腈分別以其中一個氮以橋接的方式皆在雙鉬金屬上，另一個則以η1的形式配位於鉬金屬上，得到錯合物[μ-κ1-N:μ-κ2-N-(C6H5CN)2]2Mo2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (12)。
錯合物1與白磷反應可以得到環-P5配位在雙鉬金屬上的二聚體(μ-η2:η2-P5)2[Mo2{μ-κ2-N-HC(2,6-iPr2C6H3)2}2]2 (15)，將錯合物15與鉀石墨反應，使磷-磷鍵斷裂，得到第一個環-P5陰離子(cyclo-P5 anion)配位在雙鉬金屬上的錯合物(μ-[K222-cryptand][Mo2(μ-η2:η2-P5){μ-κ2-N-HC(2,6-iPr2C6H3)2}2] (16)
This thesis reports reactions of the amidinate-supported quintuply bonded dimolybdenum complex, Mo2[μ-2-HC(N-2,6-iPr2C6H3)2]2 (1), with various aza-containing arenes, nitriles, and P4.
Two different products was obtained from the reaction of 1 and 2,2'-bipyridine, Mo2(μ-η2-1,2:η2-4,5-C10H8N2)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (2) and (η2-C10H8N2)2Mo2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (3). In complex 3, 2,2'-bipyridine coordinated to Mo centers via its lone pairs of nitrogen atoms, which is the usual coordination mode of the aza-containing arenes. By contrast, 2,2'-bipyridine of 2 coordinates to Mo centers through an η4-bonding mode. Treatment of 1 with isoquinoline, quinoxaline, or quinoline generated the quadruply bonded dimolybdenum compounds, Mo2(μ-η2-1,2:κ1-4-R)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (R = C9H7N (4), C8H6N2(5)), and Mo2(H)(μ-κ2-C9H7N)[μ-κ2-HC(N-2, 6-iPr2C6H3)2]2 (6), respectively. It is interesting to note that both complexes 4 and 5 contain η3-bound arene ligands, while C-H bond activation was oberved in complex 6.
The reactions of 1 with methy-l-4-cyanobenzoate, 4-methoxybenzonitrile, or 1,8-naphthalenedicarbonitrile led to the isolation of [2+2+2] cycloaddition products: Mo2[μ-κ2-NC(R)C(R)N][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (R = C6H4CO2CH3 (7), C6H4OCH3 (8), C5H3 (9)), respectively. On the other hand, 1 reacted with 4-(dimethylamino)benzonitrile to yield C-H bond activation product [κ1-NCC6H4N(CH3)2][μ-κ1-NC(H)C6H4NH(CH3)2]Mo2[μ-κ2-HC(N-2,6-iPr2C6H3) (N-2-iPr-6-CH(κ1-CH2)CH3-C6H3][μ-κ2-HC(N-2,6-iPr2C6H3)2] (10). It is noteworthy that we isolated interesting compounds (C16H8)(μ-κ2-N2)2{Mo2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2}2 (11) and [μ-κ1-N:μ-κ2-N-(C6H5CN)2]2Mo2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (12) from the reactions of 1 with 1,2-benzenedicarbonitrile, or [1,1'-biphenyl]-2,2'-dicarbonitrile, respectively.
Moreover, we successfully synthesized a novel cyclic-P5 bound dimolybdenum dimer, (μ-η2:η2-P5)2[Mo2{μ-κ2-N-HC(2,6-iPr2C6H3)2}2]2 (15). Further reduction of complex 15 by KC8 led to the formation of the first cyclo-P5 anion coordinated dimolybdenum complex, (μ-[K222-cryptand][Mo2(μ-η2:η2-P5){μ-κ2-N-HC(2,6-iPr2C6H3)2}2].
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