臺灣博碩士論文加值系統

本研究探討S,N,O希夫鹼配位基前驅物與醋酸鎳及醋酸鋅之反應，合成一系列含三牙配位基之金屬錯合物 (1-9)，並探討在配位基(L1H-L6H) 的苯酚基之電子效應及立體障礙對錯化合物活性之影響。錯合物經由元素分析、紅外線光譜儀與液相層析串聯質譜確定其結構組成，並利用紫外光/可見光光譜和熔點測定儀探討其物理性質。其中，錯合物1、2、4、7經X-光單晶繞射儀鑑定發現有四種不同構型，分別為五核六配位鎳錯合物1、三核六配位鎳錯合物2b、單核六配位鎳錯合物4及雙核五配位鋅錯合物7。在助催化劑 (Bu4NCl) 存在，鎳錯合物2及鋅錯合物8對環氧環己烷與二氧化碳之共聚合反應均具有良好之催化活性及小分子環碳酸酯選擇性。

A series of novel nickel and zinc acetate complexes (1-9) supported by S,N,O-tridentate Schiff-base ancillary ligands bearing substituents with electronic or steric effect have been synthesized. The composition of complexes have been characterized by elemental analysis, FT-IR and LC/MS spectroscopy. Their physical properties were investigated using UV/Vis spectroscopy and a melting point analyzer. X-ray diffraction studies of 1、2b、4 and 7 indicate that these complexes have a variety of geometry such as pentanuclear five-coordinated nickel center, trinuclear six-coordinated nickel center, mononuclear six-coordinated nickel center and binuclear five-coordinated zinc center. In the presence of Bu4NCl as a cocatalyst, nickel complex 2 and zinc complex 8 show efficient activity and high selectivity in the reaction of carbon dioxide with cyclohexene oxide yielding high yield of cis-CHC.

國立中興大學一百零五學年度碩士學位論文摘要 i
Abstract ii
目錄 iii
圖目錄 v
表目錄 viii
第一章 緒論 1
一、前言 1
二、生物可分解之材料 3
三、二氧化碳/環氧化物之共聚合反應(Copolymerization) 6
四、催化劑之研發與設計 15
五、二氧化碳與環氧化物共聚合反應之文獻回顧 16
1. 輔助配位基之金屬錯合物共聚合反應 16
2. Schiff-base錯合物之開環共聚合反應應用 24
3. 本論文Schiff-base金屬錯合物之設計方向 30
第二章 實驗部分 31
一、儀器鑑定 31
二、藥品及溶劑處理 35
三、操作技巧 39
四、S,N,O-三牙希夫鹼配位基前驅物之製備 40
五、錯合物之合成 47
六、二氧化碳/環氧化合物偶合反應之實驗步驟 54
第三章 結果與討論 55
一、配位基與錯合物之合成 55
二、鋅錯合物(7-9)之1H NMR光譜鑑定 58
三、錯合物之X-ray單晶繞射結構鑑定 59
四、錯合物之光譜研究 67
五、CO2/環氧化物(Epoxide)開環共聚合反應 77
第四章 結論 89
第五章 參考文獻 91
第六章 附錄 95

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