氫氣為不具極性之分子，因此其化學反應性相對穩定，然而將氫氣活化形成Hydride及Proton後，具有極大的利用價值。近年來由於工業快速發展導致能源耗竭及環境污染，因此我們急需一個可永續利用且不對環境造成更多負擔的替代能源，氫能的利用正好滿足這個需求。本研究將路易士酸鹼對的概念應用於氫氣的活化，藉由合成鈷金屬錯合物結合具立體障礙之路易士酸鹼(Frustrated Lewis Pairs)，探索其對氫氣活化之化學反應性。
Co_C(P) [C41H39P3CoII(CH3CN)2], Co_N(P) [C39H36NP3CoII(CH3CN)2] and Co_Si(P) [C40H39P3SiCoII(CH3CN)2]皆為五配位鈷金屬錯合物，其中C(P)為C41H39P3、N(P)為C39H36NP3、Si(P)為C40H39P3Si，配位基為三牙磷配位基與兩個乙腈溶劑。鈷金屬錯合物皆由X-ray單晶繞射鑑定其化學結構。為了可以準確探討不同路易士酸鹼模式對氫氣活化的效應，我們以五種不同路易士酸鹼的搭配與氫氣進行反應：i) Co(I) + B(C6F5)3；ii) Co(II) + B(C6F5)3；iii) Co(II) + P(t-Bu)3；iv) Co(III) + P(t-Bu)3；v) Co(III)-hydride + B(C6F5)3並應用於不飽和雙鍵之氫化反應，進行氫化反應之受質為N-benzylideneaniline (C=N雙鍵)與acetophenone (C=O雙鍵)。氫氣活化與不飽和雙鍵之氫化反應皆經由吸收光譜與核磁共振光譜鑑定其反應結果。

Hydrogen is a nonpolar molecule, so its chemical reactivity is relatively stable. However, it has great value after hydrogen is activated to form proton and hydride. In recent years, the rapid development of industry leads to energy depletion and environmental pollution. We urgently need an alternative energy that can be used sustainably and does not bring more burden to our environment. The utilization of hydrogen energy just meets the demand. In this research, we have synthesized the cobalt complexes combined with frustrated Lewis pairs for studying their reactivity to hydrogen activation.
Co_C(P) [C41H39P3CoII(CH3CN)2], Co_N(P) [C39H36NP3CoII(CH3CN)2] and Co_Si(P) [C40H39P3SiCoII(CH3CN)2] are described as five-coordinate cobalt complexes, chelated with triphos tridentate ligand and with two coordinated acetonitrile ligand, characterized by single-crystal X-ray diffraction, UV-vis, NMR and EPR. In order to accurately study the effect of Lewis acid-base on hydrogen activation, we design the modes, Co(I) + B(C6F5)3, Co(II) + B(C6F5)3, Co(II) + P(t-Bu)3, Co(III) + P(t-Bu)3 and Co(III)-hydride + B(C6F5)3, which are applied to the hydrogenation of unsaturated double bonds, N-benzylideneaniline (C=N double bond) and acetophenone (C=O double bond). The results of hydrogen activation and hydrogenation of unsaturated double bonds are characterized by UV-vis and NMR
spectroscopy.

研究生學位論文審定書......................................................................................i
研究生學位論文授權書......................................................................................ii
中文摘要...........................................................................................................iii
Abstract............................................................................................................iv
目錄...................................................................................................................v
圖目錄..............................................................................................................vi
表目錄.............................................................................................................xiii
第一章 緒論.......................................................................................................1
1-1 能源危機與環境汙染…………………………………………………………….1
1-2 碳循環…………………………………………………………………………….5
1-3 氫氣活化之探討………………………………………………………………...10
1-4 文獻探討………………………………………………………………………...23
1-5 研究方向及實驗設計…………………………………………………………...26
第二章 實驗部分...............................................................................................30
2-1 一般實驗………………………………………………………………………...30
2-2 儀器……………………………………………………………………………...30
2-3 藥品……………………………………………………………………………...32
2-4 化合物合成與鑑定……………………………………………………………...33
第三章 結果與討論...........................................................................................45
3-1 配位基C(P)、N(P)及Si(P)之合成及鑑定…………………………………..…45
3-2 鈷金屬錯合物Co_C(P)、Co_Si(P)與Co_N(P)之合成及鑑定……………....54
3-3 鈷金屬錯合物Co(I)與Co(III)之合成與鑑定…………………………………...80
3-4 氫氣活化之反應性探討………………………………………………………...87
3-5 氫氣活化應用於亞胺氫化反應之反應性探討………………………….….…112
3-6 氫氣活化應用於酮類氫化反應之反應性探討…………………………….….132
第四章 結論.....................................................................................................150
第五章 參考資料…………………………………………………………………....152
第六章 附錄.....................................................................................................154

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