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標題: S,N,O-希夫鹼三牙配位基鎳及鋅錯合物之合成、結構鑑定及其於環氧化物與二氧化碳反應之催化研究
Synthesis and Characterization of S,N,O-Tridentate Schiff Base Nickel and Zinc Complexes and Their Catalytic Studies in the Reaction of Epoxides with Carbon Dioxide
作者: 王姵今
Pei-Chin Wang
關鍵字: 希夫鹼;二氧化碳;催化;環氧化物;Schiff Base;Carbon Dioxide;Catalyst;Epoxides
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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.
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