臺灣博碩士論文加值系統

將[PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)]與NH3反應，以莫耳比1:10的比例可確保合成出[NiIII (NH3)(P(o-C6H3-3-SiMe3-2-S)3)] (1)。另外，也藉由18-crown- 6-ether的與NH3作用形成氫鍵以及體積大利於堆疊的特性成功得到化合物1的晶體。由於NH3只是單純提供孤對電子與金屬做鍵結，所以相較於帶有負電的配位基與金屬形成較強的鍵結，化合物1的NH3較易被其他外加親和基所置換，因此可利用其性質較方便合成出預計的化合物。
將[PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)]與N2H4(aq)反應，以莫耳比1:10的比例可確保合成出[PPN][NiII (N2H4)(P(o-C6H3-3-SiMe3-2-S)3)] (2)。同時利用化合物1末端配位基容易離去的特性，合成出預想的[K][NiIII(OH)(P(o-C6H3-3-SiMe3- 2-S)3)]並對其在合成化合物2中所扮演的關鍵中間物做探討。由於化合物2不僅含有易離去的配位基且擁有較為活潑的電子環境，也因此有機會當作活化小分子的平台。而從將化合物2通入NO後的結果得到[PPN][NiIII (NO2)(P(o-C6H3-3- SiMe3-2-S)3)]則被視為最有可能達成活化小分子的目的。

Complex [NiIII(NH3)(P(o-C6H3-3-SiMe3-2-S)3)] (1) was synthesized by reaction of [PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)] and NH3 in 1:10 molar ratio. Besides, addition of 18-crown-6-ether assisted the formation of crystals by hydrogen bonds with terminal NH3 and its bulky sizes. The terminal ligand, NH3, can be easily replaced by the incoming nucleophiles due to its weak bonding compared to the strong interaction between metal center and other ligands bearing negative charges. As a result, taking the advantage of its lability, we could synthesize the expected complexes via replacement.
Reaction of [PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)] and N2H4 (aq) in 1:10 molar ratio afforded [PPN][NiII(N2H4)(P(o-C6H3-3-SiMe3-2-S)3)] (2). [K][NiIII(OH)- (P(o-C6H3-3-SiMe3-2-S)3)] was synthesized by using the lability of NH3 ligand of complex 1. The hydroxyl ligand coordinated to nickel center is also proven to be the key intermediate responsible for the formation of complex 2. Owning to its labile ligand and active electronic environment of complex 2, it could serve as a platform for activation of small molecules. The successful result among small molecules is that purging NO into the solution of complex 2 led to the formation of [PPN][NiIII (NO2)(P(o-C6H3-3- SiMe3-2-S)3)].

第一章 緒論 1
1-1小分子活化 1
1-2一氧化二氮 (N2O) 2
1-3氧氣 (O2) 5
1-4二氧化碳 (carbon dioxide) 以及二硫化碳 (carbon disulfide) 10
1-5 研究方向 17
第二章 實驗部分 18
2-1 一般實驗 18
2-2 儀器 18
2-3 藥品 19
2-4 化合物的合成及鑑定 20
2-4-1合成[Ni(NH3)(P(o-C6H3-3-SiMe3-2-S)3)] (1) 20
2-4-2合成[PPN][Ni(N2H4)(P(o-C6H3-3-SiMe3-2-S)3)] (2). 20
2-5 化合物的反應 21
2-5-1 [Ni(NH3)(P(o-C6H3-3-SiMe3-2-S)3)]與KOH的反應 21
2-5-2 [K-18-crown-6-ether][Ni(OH)(P(o-C6H3-3-SiMe3-2-S)3)]與N2H4(THF)反應 22
2-5-3 [K-18-crown-6-ether][Ni(OH)(P(o-C6H3-3-SiMe3-2-S)3)]與CO的反應 22
2-5-4 [PPN][Ni(N2H4)(P(o-C6H3-3-SiMe3-2-S)3)]與CO的反應 22
2-5-5 [Ni(P(o-C6H3-3-SiMe3-2-S)3)]2 與N2H4(THF)的反應 23
2-5-6 [Ni(P(o-C6H3-3-SiMe3-2-S)3)] 2 與N2H4(aq)的反應 23
2-5-7 [Ni(NH3)(P(o-C6H3-3-SiMe3-2-S)3)]與[PPN][Cl]的反應 24
2-5-8 [PPN][Ni(N2H4)(P(o-C6H3-3-SiMe3-2-S)3)]與NO的反應 24
2-5-9 [Ni(N2H4)(P(o-C6H3-3-SiMe3-2-S)3)]與KC8的反應 24
2-6 晶體結構解析(Crystallography) 26
第三章 結果與討論 29
3-1 化合物[Ni(NH3)(P(o-C6H3-3-SiMe3-2-S)3)] (1)的合成、結構與光譜分析 29
3-2 化合物[PPN][Ni(NH2NH2)(P(o-C6H3-3-SiMe3-2-S)3)] (2)的合成、結構與光譜分析 38
3-3 [NiIII(NH3)(P(o-C6H3-3-SiMe3-2-S)3)] (1)和[cation][NiII(NH2 - NH2)(P(o-C6H3-3- SiMe3-2-S)3)] (2)其他合成方法 (cation = N2H5, K) 50
3-4 [NiIII(NH3)(P(o-C6H3-3-SiMe3-2-S)3)] (1)對[PPN][Cl]之反應性 51
3-5 [PPN][NiII(NH2NH2)(P(o-C6H3-3-SiMe3-2-S)3)] (2)對CO之反應性 52
3-6 [PPN][NiII(NH2NH2)(P(o-C6H3-3-SiMe3-2-S)3)] (2)對NO之反應性 53
3-7 [PPN][NiII(NH2NH2)(P(o-C6H3-3-SiMe3-2-S)3)] (2)對小分子之反應性 56
第四章 結論 57
Reference 59

圖目錄

Figure 1-1. 科學家所推斷N2O 經由金屬酵素的代謝過程 3
Figure 1-2. N2O與 Frustrated Lewis Pair 鍵結圖 3
Figure 1-3. N2O不同的鍵結模式(a,b,c = 2,3,4 當量的Zn(C6F5)2 ) 4
Figure 1-4. N2O與vanadium反應所形成的化合物 4
Figure 1-5. 氧分子的MO軌域圖 5
Figure 1-6. 血藍蛋白與氧氣反應之示意圖 6
Figure 1-7. Karlin教授所合成的model compound 6
Figure 1-8. Tolman教授所合成的model compound 7
Figure 1-9. 氧氣鍵結在血紅蛋白之示意圖 7
Figure 1-10. Collman教授所合成的model compound 8
Figure 1-11. 第一例Cr(III)-superoxo的單晶結構 9
Figure 1-12. 利用Cr(III)-superoxo達到C-H鍵的活化及氧原子的轉移 9
Figure 1-13. CO dehydrogenase (CODH) 10
Figure 1-14. CO dehydrogenase 的反應機制 11
Figure 1-15. 各種CS2鍵結模式 12
Figure 1-16. Stolzenberg教授所發表的異核金屬錯合物 12
Figure 1-17. Simpson教授將CS2活化的例子 13
Figure 1-18. Hillhouse教授將CS2活化的例子 14
Figure 1-19. Limberg教授將CS2活化的例子 14
Figure 1-20. Meyer教授將CS2活化的例子 15
Figure 1-21. Dong教授將CO2完成催化的機制 16
Figure 1-22. Bouwman教授將CO2完成催化的機制 16

Figure 3-1. 化合物 1 UV/vis光譜 (THF) 34
Figure 3-2. 化合物 1 與18-crown-6-ether氫鍵作用之示意圖 34
Figure 3-3. 化合物 1 X-ray結構ORTEP圖 35
Figure 3-4. 化合物 1溶於THF之EPR訊號 36
Figure 3-5. 化合物 1 SQUID資料 37
Figure 3-6. [NiIII (NH2NH2)(P(o-C6H3-3-SiMe3-2-S)3)] UV/vis光譜 (THF-CH3CN) 42
Figure 3-8. 化合物 2 UV/vis光譜 (THF-CH3CN) 46
Figure 3-9. 化合物 2 X-ray結構ORTEP圖 47
Figure 3-10. 化合物 2溶於THF-CH3CN之EPR訊號 48
Figure 3-11. 化合物 2 SQUID資料 49
Figure 3-12. [NiII (CO)(P(o-C6H3-3-SiMe3-2-S)3)] IR光譜 (THF) 53
Figure 3-13. N2O的IR光譜(2222 cm-1) (THF-CH3CN) 55

表目錄


Table 2-1. Crystallographic Data of [18-crown-6-ether][Ni(NH3)(P(o-C6H3-3-SiMe3-2-S)3)] (1) 27
Table 2-2. Crystallographic Data of [PPN][Ni(N2H4)(P(o-C6H3-3-SiMe3-2-S)3)] (2) 28
Table 3-1. 化合物1重要鍵長(Å)、鍵角(°) 35
Table 3-2. 化合物2重要鍵長(Å)、鍵角(°) 47
Table 3-3. 各化合物鍵長比較(Å) 39

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