本研究探討一系列含S,N,O-希夫鹼配位基前驅物與二乙基鋅與氯化鎳之反應，合成三牙配位基之金屬錯合物 (1)-(8)，並探討在苯酚基上配位基 (L1H - L4H) 之電子效應及立體障礙對錯化合物活性之影響。錯合物經由核磁共振儀、紅外線光譜儀確定其結構組成，並利用紫外光/可見光光譜、熔點測定儀探討其物理性質。錯合物2、6經X-光單晶繞射儀鑑定其晶體結構，皆為六配位單核雙取代的結構。配位基前驅物與金屬之一鍋化催化在外加助催化劑 (Bu4NBr) 條件下，配位基前驅物與醋酸鋅、醋酸鎳對環氧環己烷與二氧化碳之一鍋化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 zinc and nickel complexes (1) - (8) supported by S,N,O-tridentate Schiff-base ancillary ligands (L1 - L4) bearing substituents with various electronic or steric effect have been synthesized. The composition of complexes were structurally characterized by FT-IR and NMR spectroscopy. Their physical properties were investigated using UV/Vis spectroscopy and melting point analyzer. X-ray diffraction studies of 2 and 6 indicate that both complexes are mononuclear with six-coordinated metal center. All of zinc and nickel complexes show efficient activity and high selectivity to the reaction of CHO and CO2 in the presence of 1:1 ratio of ligands and existence of Bu4NBr as a co-catalyst yielding cis-CHC.

目錄
國立中興大學一百零八學年度碩士學位論文摘要................................ i
Abstract................................ ................................ ................................ ...... ii
目錄................................ ................................ ................................ ........... iii
圖表目錄................................ ................................ ................................ ..... v
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................................ ................................ 13
五、二氧化碳與環氧化物共聚合反應之文獻回顧....................... 15
第二章 實驗部分................................ ................................ .................... 28
一、儀器鑑定................................ ................................ .................... 28
二、藥品及溶劑處理................................ ................................ ........ 31
三、操作技巧................................ ................................ .................... 34
四、S,N,O-三牙希夫鹼配位基前驅物之製備................................ 35
五、錯合物之合成................................ ................................ ............ 39
六、二氧化碳/環氧化合物偶合反應之實驗步驟.......................... 45
第三章 結果與討論................................ ................................ ................ 46
一、配位基前驅物與錯合物之合成................................ ............... 46
二、錯合物之光譜鑑定................................ ................................ .... 49
三、錯合物之X-ray單晶繞射結構鑑定................................ ........ 53
四、CO2/環氧化物(Epoxide)開環偶合反應............................... 57
第四章 結論................................ ................................ ............................. 68
第五章 參考文獻................................ ................................ .................... 69
第六章 附錄................................ ................................ ............................. 72
附錄一、配位基及錯合物之1H、13C NMR 光譜 ......................... 72
附錄二、配位基及錯合物之IR光譜................................ ............. 81
附錄三、錯合物之晶體資料................................ ........................... 85

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