臺灣博碩士論文加值系統

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.

第一章 緒論 1
1-1 金屬-金屬鍵的發展 1
1-2 雙金屬五重鍵錯合物 3
1-3 低配位數低價數之雙金屬五重鍵錯合物與小分子的反應 7
1-4 雙鎢金屬多重鍵錯合物的發展 8
1-5 研究目的與方向 10
第二章 追求雙鎢金屬五重鍵錯合物 11
2-1 前言 11
2-2 錯合物W2Cl6(DME)2 (2)的合成 14
2-3 錯合物W2(μ-Cl)Cl2[μ-κ2-PhC(N-2,6-iPr2C6H3)2]2 (3)的合成與鑑定 15
2-4 錯合物W2(μ-Cl)[Cl2Li(OEt2)][μ-κ2-PhC(N-2,6-iPr2C6H3)2]2 (4)的合成與鑑定 18
2-5 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)的合成與鑑定 24
2-6 錯合物WCl4(κ2-2,6-iPr2C6H3-DAB) (6)的合成 28
2-7 錯合物W2(μ-Cl)3Cl2(κ2-2,6-iPr2C6H3-DAB)2 (7)的合成與鑑定 30
2-8 錯合物W2(μ-Cl)2Cl4(N-2,6-iPr2C6H3)[κ2-2,6-iPr2C6H3-DAB(Me, Me)] (8)的合成與鑑定 33
2-9 錯合物W2(μ-Cl)Cl2[μ-(κ1;κ2)-C(CH2)3O][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (9)的合成與鑑定 36
2-10 錯合物W2(μ-Cl)Cl4[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (10)的合成與鑑定 44
2-11 結論 46
第三章 實驗流程 47
3-1 一般操作 47
3-2 實驗使用儀器 47
3-3 實驗溶劑與藥品 48
3-3-1 溶劑 48
3-3-2 實驗藥品 48
3-4 實驗步驟 49
3-4-1 W2Cl6(DME)2 (2)的合成 49
3-4-2 W2(μ-Cl)Cl2[μ-κ2-PhC(N-2,6-iPr2C6H3)2]2 (3)的合成 49
3-4-3 W2(μ-Cl)[Cl2Li(OEt2)][μ-κ2-PhC(N-2,6-iPr2C6H3)2]2 (4)的合成 50
3-4-4 W2(μ-H)2[μ-κ2-PhC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(κ1-CH2)CH3-C6H3)]2 (5)的合成 50
3-4-5 WCl4(κ2-2,6-iPr2C6H3-DAB) (6)的合成 52
3-4-6 W2(μ-Cl)3Cl2(κ2-2,6-iPr2C6H3-DAB)2 (7)的合成 52
3-4-7 W2(μ-Cl)2Cl4(N-2,6-iPr2C6H3)[κ2-2,6-iPr2C6H3-DAB(Me, Me)] (8)的合成 53
3-4-8 W2(μ-Cl)Cl2[μ-(κ1;κ2)-C(CH2)3O][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (9)的合成 54
3-4-9 W2(μ-Cl)Cl4[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (10)的合成 55
第四章 其他嘗試 56
4-1 錯合物3a的合成 56
4-2 含二茂鐵之雙氮基脒配基之合成 57
4-2-1 前言 57
4-2-2 FcLi2(TMEDA) (11a)的合成 58
4-2-3 FcBr2 (11b)的合成 59
4-2-4 Fc(N3)2 (11c)的合成 60
4-2-5 Fc(NH2)2 (11d)的合成 61
4-2-6 Fc(NHAc)2 (11e)的合成 62
第五章 參考資料 63
第六章 附錄 68
6-1 W2(μ-Cl)Cl2[μ-κ2-PhC(N-2,6-iPr2C6H3)2]2 (3)的晶體結構資料 68
6-2 W2(μ-Cl)[Cl2Li(OEt2)][μ-κ2-PhC(N-2,6-iPr2C6H3)2]2 (4)
的晶體結構資料 69
6-3 W2(μ-H)2[μ-κ2-PhC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH
(κ1-CH2)CH3-C6H3)]2 (5)的晶體結構資料 70
6-4 W2(μ-Cl)3Cl2(κ2-2,6-iPr2C6H3-DAB)2 (7)的晶體結構資料 71
6-5 W2(μ-Cl)2Cl4(N-2,6-iPr2C6H3)[κ2-2,6-iPr2C6H3-DAB(Me, Me)] (8)
的晶體結構資料 72
6-6 W2(μ-Cl)Cl2[μ-(κ1;κ2)-C(CH2)3O][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (9)
的晶體結構資料 73
6-7 W2(μ-Cl)Cl4[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (10)的晶體結構資料 74
 

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