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研究生:王子元
研究生(外文):Wang, Zi-Yuan
論文名稱:二硫化碳配位之鎳(III)錯合物合成研究
論文名稱(外文):The formation of η2-CS2-bound Ni(III) complex
指導教授:廖文峯
指導教授(外文):Liaw, Wen-Feng
學位類別:碩士
校院名稱:國立清華大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2013
畢業學年度:101
語文別:中文
論文頁數:76
中文關鍵詞:二硫化碳二氧化碳活化
外文關鍵詞:carbon disulfidecarbon dioxideNickelactivation
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以實驗室先前合成的P(C6H3-3-SiMe3-2-S)3能產生出一系列鎳三價
錯合物為想法出發,改合成出P(C6H4-2-N(CH3)2)3,期許能以其產生出鎳一價錯合物,並研究其對小分子的活化。
將NiII(ClO4)2•6H2O等比例加入P(C6H4-2-N(CH3)2)3並溶於MeCN中,於室溫、氮氣環境下可以得到[NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][ClO4]2 (1),利用X-ray單晶繞射解析、超導量子干涉儀、電子順磁共振光譜儀、核磁共振儀、IR光譜儀和UV-Vis光譜儀鑑定錯合物1,可知鎳金屬為正二價high-spin且含兩個未成對電子,六配位扭曲的八面體結構。此外,可改用Ni粉及[NO][BF4]溶於MeCN中,合成出[Ni(NCMe)6][BF4]2,再與等比例的P(C6H4-2-N(CH3)2)3反應後得到[NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2 (2),來達成改變陰離子的目的。
將錯合物1或2與當量的KC8於低溫、氮氣下的環境反應可以生成[NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X = ClO4或BF4) (3),利用UV-Vis與EPR光譜可以測得錯合物3的訊號,發現錯合物3對氧氣敏感,並推測其Ni中心金屬只與ligand上之P原子及兩個solvent (-NCCH3)的氮原子有配位,形成扭曲平面三角形結構。在活化小分子方面,錯合物3可和CS2、CO2反應,推測會產生[NiIII(η2-CS2)(P(C6H4-2-N(CH3)2)3)]及[NiIII(η2-CO2)(P(C6H4-2-N(CH3)2)3)],由UV-Vis光譜及EPR來鑑定產物。
將[NiIII(η2-CS2)(P(C6H4-2-N(CH3)2)3)]加入等當量的KC8於低溫、氮氣下反應,得到[NiII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] (4),利用X-ray、UV-Vis、IR、1H NMR鑑定錯合物4的鎳金屬為正二價low-spin,四配位扭曲的平面四邊形結構。

The previously synthesized P(C6H3-3-SiMe3-2-S)3 can serve as a ligand to produce a series of nickel(III) complexes.Here we synthesize P(C6H4-2-N(CH3)2)3, expected to produce Ni(I) complex, and study its effect on the activation of small molecules.
The NiII(ClO4)2 • 6H2O reacting with P(C6H4-2-N(CH3)2)3 (1:1 molar ratio) in MeCN at room temperature under dinitrogen atmosphere yielded complex [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)] [ClO4]2 (1). Complex 1, characterized by single-crystal X-ray diffraction, SQUID, EPR, 1H NMR, IR and UV-Vis, was demonstrated to be mononuclear high-spin Ni(II) complex, containing two unpaired electrons. The geometry of the Ni center is a six-coordinate distorted octahedral complex. In addition, Ni powder and [NO][BF4] were reacted to synthesize [Ni(NCMe)6][BF4]2. Reaction of [Ni(NCMe)6][BF4]2 with an equal proportion of P(C6H4-2-N(CH3)2)3 yielded complex [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2 (2).
Complexes 1 or 2 reacting with the equivalent of KC8 at low temperatures under dinitrogen atmosphere, respectively, yielded complex [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X = ClO4or BF4) (3). Complex 3 was sensitive to dioxygen and was characterized by UV-Vis and EPR spectroscopy. In the activation of small molecules, compound 3 may react with CS2 or CO2, to yield [NiIII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] or [NiIII(η2-CO2)(P(C6H4-2-N(CH3)2)3)], characterized by UV-Vis and EPR.
The [NiIII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] reacting with KC8 in 1:1 molar ratio at low temperatures under dinitrogen atmosphere produced [NiII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] (4). Complex 4, characterized by X-ray, UV-Vis, IR, 1H NMR, was low-spin Ni(II) complex.The geometry of the Ni center is a four-coordinate distorted square-planar complex.

目錄
第一章、緒論 9
1-1 前言 9
1-2 二氧化碳(CO2)之性質 10
1-2-1 分子幾何 10
1-2-2 光譜性質 12
1-2-2-1 Infrared(IR) 12
1-2-2-2 UV-Vis 12
1-2-2-3 13C-Nuclear Magnetic Resonance(NMR) 12
1-2-3 物理、化學性質與安全性 13
1-3 CO2與金屬中心的配位及反應 14
1-3-1 配位模式 14
1-3-2 CO2配位過渡金屬系統之反應性 15
1-4 鎳(Nickel)為中心之活化CO2的研究 17
1-5 鎳(Nickel)為中心之活化二氧化硫(CS2)的研究 19
1-6 研究方向 24
第二章、實驗部分 25
2-1 一般實驗 25
2-2 儀器 26
2-3 藥品 27
2-4 Ligand的合成 28
2-5 錯合物的合成及鑑定 30
1. 合成[NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][ClO4]2 (1) 30
2. 合成[NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2 (2) 30
3. 合成[NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X=BF4 or ClO4) (3) 31
4. 合成[NiII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] (4) 32
2-6錯合物的反應 33
1. [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2與O2/CO/N2O/CO2的反應 33
2. [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2與CS2的反應 33
3. [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2與KO2的反應 33
4. [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X=BF4 or ClO4) 與O2的反應 34
5. [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] 與CO / N2O的反應 34
6. [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] 與CS2的反應 35
7. [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] 與CO2的反應 35
2-7 晶體結構解析(Crystallography) 37
第三章、結果與討論 40
3-1 P(C6H4-2-N(CH3)2)3的合成、結構和光譜分析 40
3-2 [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][ClO4]2 (1) 與[NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2 (2) 的合成、結構和光譜分析 42
3-3 [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X=BF4 or ClO4) (3)的合成與光譜分析 51
3-4 [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X=BF4 or ClO4) (3)與CS2、CO2的反應 56
3-5 [NiII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] (4) 的合成、結構和光譜分析 60
第四章、結論 68
Reference 70


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