臺灣博碩士論文加值系統

使用吡唑 (HPz) 及有機腈類分子藉由鎳金屬離子進行偶合反應，合成一系列的吡唑亞胺基含鎳離子錯合物。四倍量的吡唑與二倍量乙腈加上一倍量的三種鎳金屬離子形成中間錯合物 [Ni(CH3CN)2(HPz)4][X-] (X-= ClO4- (1)，BF4- (5)，NO3- (9))，而錯合物1、9會持續反應成為錯合物 [Ni(HPz)2(HN=C(CH3)Pz)2][X-] (X- = ClO4- (2)，NO3- (10))。而錯合物5則需添加少許三乙基胺使其反應成錯合物[Ni(HPz)2(HN=C(CH3)Pz)2][BF4-] (6)。而乙腈分子可替換成丙腈或是苯甲腈，一樣可以形成吡唑亞胺基含鎳離子錯合物。經由以上反應，及探討 IR 光譜、 UV 光譜及 X-ray 結構推測出新的過渡態。
合成有機配位基 2-(o-methylthiophenyliminomethyl)pyrrole (MeLH) (13) 且詳細鑑定，並與 Co2+、Co3+、Fe2+、Ni2+、Cu2+ 五種不同金屬離子反應，得到錯合物M2+(MeL)2 (M2+=Ni2+ (14)，Cu2+ (15)、Fe2+ (16)、Co2+ (17))，Co3+(MeL)3 (18)，及Co3+(MeL)(L) (19)。錯合物14在不同結晶環境下可以得到同分異構物14a及14b；錯合物19 為錯合物18 進行S-C鍵的斷裂形成。而錯合物14-19皆以 NMR、IR、UV、EPR、ESI-MS 及 X-ray 的鑑定分析探討其性質。

Abstract
By using the coupling reaction between pyrazole (HPz) and organic nitrile (RCN) mediated by Ni2+ ions, a series of pyrazolylamidinonickel complexes were synthesized. When four equivalent of HPz and one equivalent of [Ni(MeCN)6][X-] (X-= ClO4-, BF4- , or NO3-) were stirred in MeCN, complexes [Ni(MeCN)2(HPz)4][X-] (X-= ClO4- (1)，BF4- (5)，NO3- (9)) were obtained immediately, which serve as the intermediates for the coupling reaction. Although the isomerization of complexes 1 and 9 to complexes [Ni(HPz)2(HN=C(Me)Pz)2][X-] (X- = ClO4- (2), NO3- (10)) occurs slowly at room temperature, the coupling reaction in complex 5 does not happen without the aid of weak base NEt3. The reaction is also successfully conducted with other nitriles RCN bearing electron-donating group (R = Et, Bz). Based on the effects of counter anion on the rate of coupling reaction, solution IR, UV-vis spectroscopies, and X-ray crystal structure determination, a mechanism based on anion-mediated/hydrogen-bonding-driven proton transfer for the coupling reaction is proposed.
Besides, we synthesized and characterized a new N2S organic ligand 2-(o-methylthiophenyliminomethyl)pyrrole (MeLH) (13), and tested the coordination reactivity toward transition metal ions Co2+, Co3+, Fe2+, Ni2+, and Cu2+. A series of metal complexes bearing this ligand were obtained: M2+(MeL)2 (M2+=Ni2+ (14), Cu2+ (15), Fe2+ (16), Co2+ (17)), Co3+(MeL)3 (18), and Co3+(MeL)(L) (19). Two stereo-isomers of complex 14 were gained, depending on the crystallization conditions. Complex 19 is the reaction product of complex 18 exposed under UV light. All complexes 13-19 were characterized by NMR, IR, UV-vis, EPR, EA, ESI-MS, and X-ray analyses. The properties of these complexes with MeLH ligand were also discussed in this report.

目錄
第一章 序論 1
1-1 利用吡唑亞胺基為配位基之錯化合物 1
1-2 含 N2S 三芽有機配位基及含金屬錯合物 4
第二章 實驗部份 7
2-1 一般實驗 7
2-2 物理性質的測量 7
2-3 含吡唑亞胺基為配位基之錯化合物的合成 8
2-3-1 合成[bis(acetonitrile)- tetrakis(pyrazole) nickel] [perchlorate]-----1 8
2-3-2 合成[bis[pyrazole-1-[1-(imino-κN)ethyl]-1H-pyrazole] nickel] [perchlorate]-----2 8
2-3-3 合成[bis[pyrazole-1-[1-(imino-κN)propyl]-1H-pyrazole] nickel] [perchlorate]-----3 9
2-3-4 合成[bis[pyrazole-1-[1-(imino-κN)benzyl]-1H-pyrazole] nickel] [perchlorate]-----4 9
2-3-5 合成[bis(acetonitrile)- tetrakis(pyrazole) nickel] [tetrafluoro- borate]-----5 10
2-3-6 合成[bis[pyrazole-1-[1-(imino-κN)ethyl]-1H- pyrazole] nickel] [tetrafluoroborate]-----6 10
2-3-7 合成[bis[pyrazole-1-[1-(imino-κN)propyl]-1H- pyrazole] nickel] [tetrafluoroborate]-----7 11
2-3-8 合成[bis[pyrazole-1-[1-(imino-κN)benzyl]-1H- pyrazole] nickel] [tetrafluoroborate]-----8 11
2-3-9 合成[bis(acetonitrile)- tetrakis(pyrazole) nickel] [nitrate]-----9 12
2-3-10 合成[bis[pyrazole-1-[1-(imino-κN)ethyl]-1H- pyrazole] nickel] [nitrate]-----10 12
2-3-11 合成[bis[pyrazole-1-[1-(imino-κN)propyl]-1H- pyrazole] nickel] [nitrate]-----11 13
2-3-12 合成[bis[pyrazole-1-[1-(imino-κN)benzyl]-1H- pyrazole] nickel] [nitrate]-----12 13
2-4 含 N, N, S 希夫鹼三芽基及含金屬錯合物的合成 14
2-4-1 合成2-(o-methylthiophenyliminomethyl)pyrrole-----13 14
2-4-2 合成bis[2-(o-methylthiophenyliminomethyl)pyrrole] Nickel(II)-----14 14
2-4-3 合成bis[2-(o-methylthiophenyliminomethyl)pyrrole] Cupper(II)-----15 15
2-4-4 合成bis[2-(o-methylthiophenyliminomethyl)pyrrole] Iron(II)-----16 16
2-4-5 合成bis[2-(o-methylthiophenyliminomethyl)pyrrole] Cobalt(II)-----17 16
2-4-6 合成tri[2-(o-methylthiophenyliminomethyl)pyrrole] Cobalt(III)-----18 17
2-4-7 合成 [2-(o-methylthiophenyliminomethyl)pyrrole]
[2-(o-thiophenyliminomethyl)pyrrole] Cobalt(III)-----19 17
第三章 結果與討論 18
3-1 利用吡唑亞胺基為配位基之錯化合物的合成與鑑定 18
3-1-1 錯合物1 19
3-1-2 錯合物2 21
3-1-3 錯合物5 25
3-1-4 錯合物6 27
3-1-5 錯合物9 28
3-1-6 錯合物10 29
3-1-7 錯合物1及錯合物2 UV 時間追蹤光譜 33
3-1-8 含錯合物1、5、9氫鍵 IR光譜及反應速率之比較 35
3-2 利用三芽基希夫鹼(N2S1)為配位基之錯化合物的合成與鑑定 37
3-2-1 三芽基希夫鹼(N2S1)有機配位基13 37
3-2-2 錯合物14 42
3-2-3 錯合物15 45
3-2-4 錯合物16 48
3-2-5 錯合物17 51
3-2-6 錯合物18 53
3-2-7 錯合物19 56
第四章 結論及未來展望 60
參考文獻 62
附錄 66

Scheme 目錄
Scheme 1-1-1 腈類分子與不同親核試劑的舉例偶合反應 1
Scheme 1-1-2 偶合反應的推測反應機構 3
Scheme 1-2-1 乙醯輔酶A合成酶的反應機制 5
Scheme 3-1-1 錯合物1、5、9的反應式 18
Scheme 3-1-2 含吡唑亞胺基的錯合物反應式 18
Scheme 3-1-3 錯合物8的反應式 27
Scheme 3-1-4 UV 光譜轉變之錯合物反應式 33
Scheme 3-2-1 有機配位基13反應式 37
Scheme 3-2-2 含有機配位基13之錯合物總反應式 41
Scheme 4-1 偶合反應機制的過渡態 60

Figure 目錄
Fig 1-1-1 Examples of metal-mediated additions. 2
Fig 1-2-1 Drawing of the active site of Acetyl CoA Synthase. 4
Fig 3-1-1 The molecular structure of complex 1. 20
Fig 3-1-2 The NHO hydrogen-bonding interactions of complex 1. 21
Fig 3-1-3 The molecular structure of complex 2. 22
Fig 3-1-4 Packing diagrams of complex 2 showing the - stacking and C-H bonding. 24
Fig 3-1-5 The molecular structure of complex 5. 26
Fig 3-1-6 The NHF hydrogen-bonding interactions of complex 5. 27
Fig 3-1-7 The molecular structure of complex 9. 28
Fig 3-1-8 The NHO hydrogen-bonding interactions of complex 9. 29
Fig 3-1-9 The molecular structure of complex 10 . 30
Fig 3-1-10 Packing diagrams of complex 10 showing the - stacking and C-H bonding. 32
Fig 3-1-11 The UV-vis spectrum of three nickel perchlorae complexes in MeCN. 34
Fig 3-1-12 The time-dependent changes in the UV-vis spectrum of the conversion of complex 1 to complex 2. 34
Fig 3-1-13 The IR spectrum (N-H) of pyrazole, complex 1, 5, 9 in CH3CN. 36
Fig 3-2-1 1H-13C HSQC NMR spectrum of compound 13 in CDCl3. 38
Fig 3-2-2 The molecular structure of compound 13. 38
Fig 3-2-3 The NHN hydrogen-bonding interactions of compound 13. 39
Fig 3-2-4 The molecular structure of compound 13 represented by spacefill model. 40
Fig 3-2-5 The molecular structure of complex 14a and complex 14b. 43
Fig 3-2-6 PXRD patterns of complex 14. 45
Fig 3-2-7 The molecular structure of complex 15. 46
Fig 3-2-8 Packing diagram of complex 15 showing the intramolecular C-H⋅⋅⋅π bonding interactions. 47
Fig 3-2-9 The molecular structure of complex 16. 49
Fig 3-2-10 Packing diagram of complex 16 showing the intermolecular C-H⋅⋅⋅π bonding interactions. 50
Fig 3-2-11 1H NMR spectrum of compound 16 in CDCl3. 50
Fig 3-2-12 The molecular structure of complex 17. 52
Fig 3-2-13 The molecular structure of complex 18. 54
Fig 3-2-14 Complex 18 showing the cooperative edge-to-face C-H bonding interactions. 55
Fig 3-2-15 1H NMR spectrum of compound 18 in CDCl3. 56
Fig 3-2-16 The molecular structure of complex 19. 57
Fig 3-2-17 Packing diagram of complex 19 π-π stacking and C-H⋅⋅⋅π bonding interactions. 58
Fig 3-2-18 The time-dependent ESI-MS spectra of complex 19. 59

Table 目錄
Table 3-1-1 錯合物1 重要鍵長(Å)與鍵角(°) 20
Table 3-1-2 錯合物2 重要鍵長(Å)與鍵角(°) 23
Table 3-1-3 錯合物2的C-H 及  的鍵長及鍵角 24
Table 3-1-4 錯合物5 重要鍵長(Å)與鍵角(°) 26
Table 3-1-5 錯合物9 重要鍵長(Å)與鍵角(°) 29
Table 3-1-6 錯合物10 重要鍵長(Å)與鍵角(°) 31
Table 3-1-7 錯合物10的C-H 及  的鍵長及鍵角 32
Table 3-1-8 不同陰離子所產生之氫鍵與反應速率比較 36
Table 3-2-1 配位基13 重要鍵長(Å)與鍵角(°) 39
Table 3-2-2 錯合物14a及14b重要鍵長(Å)與鍵角(°) 44
Table 3-2-3 錯合物15 重要鍵長(Å)與鍵角(°) 47
Table 3-2-4 錯合物15的C-H 的鍵長及鍵角 47
Table 3-2-5 錯合物16 重要鍵長(Å)與鍵角(°) 49
Table 3-2-6 錯合物16的C-H 的鍵長及鍵角 50
Table 3-2-7 錯合物17 重要鍵長(Å)與鍵角(°) 52
Table 3-2-8 錯合物18 重要鍵長(Å)與鍵角(°) 54
Table 3-2-9 錯合物18的C-H 的鍵長及鍵角 55
Table 3-2-10 錯合物19 重要鍵長(Å)與鍵角(°) 57
Table 3-2-11 錯合物19的C-H 的鍵長及鍵角 58

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