苯並三唑苯酚氧基及其衍生物之金屬錯合物合成、結構鑑定、光性質以及應用於環酯類開環聚合反應與二氧化碳/環氧化物偶合和共聚合反應的催化研究

Synthesis, Characterization and Optical Properties of Metal Complexes Bearing Benzotriazole Phenoxide Derivatives: Catalysis for Ring-Opening Polymerization of Cyclic Esters and Carbon Dioxide/Epoxides Coupling and Copolymerization

李晨宇(Chen-Yu Li)

指導教授 ： 林嘉和 ； 柯寶燦

中原大學/理學院/化學研究所/博士(2013年)

https://doi.org/10.6840/cycu201300356

摘要

我們成功合成一系列含苯並三唑苯酚氧基(benzotriazole phenoxide, BTP)之金屬錯合物[{(-C1BTP)AlMe2}2] (1)、[(C1BTP)2AlMe] (2)、 [(C1BTP)3Al] (3)、[(C1BTP)2Al(OAn)] (4)、[{(C1BTP)2Al}2(-O)] (5)、 [{(C1BTP)2Al(-OH)}2] (6)、[(C1BTP)Al2Me5] (7)、[(CMe2PhBTP)AlMe2] (8)、[(t-BuBTP)AlMe2] (9)、[(CMe2PhBTP)2AlMe] (10)、[{(CMe2PhBTP)2Al}2(-O)] (11)、[(TMClBTP)2Mg(THF)2] (12)、[(CMe2PhBTP)2Al(NMe2)] (13)、[(t-BuBTP)2Al(NMe2)] (14)、[(TMClBTP)2Al(NMe2)] (15)、[{(t-BuBTP)2Al}2(-O)] (16)、[{(TMClBTP)2Al}2(-O)] (17)、[{(-C8BTP)Ti(OiPr)3}2] (18)、[(C8BTP)2Ti(OiPr)2] (19)、[(t-BuBTP)2Ti(OiPr)2] (20)與[(TMClBTP)2Ti(OiPr)2] (21)以及含胺基側臂架橋之雙BTP配位基(amine-BiBTP2-)的三核金屬錯合物 [(C1NNBiBTP)2Mg3(OBn)2] (22)、[(C1PPBiBTP)2Mg3(OBn)2] (23)、 [(C1NNBiBTP)2Zn3(OAc)2] (24)、[(C1NNBiBTP)2Co3(OAc)2] (25)與 [(C1NNBiBTP)2Ni3(OAc)2(H2O)2] (26)。在光學性質研究方面，利用可見光-紫外光光譜儀及螢光光譜儀測量其吸收波長、放光波長與量子產率。由實驗結果顯示，在相同濃度下，錯合物1-3及5-7在二氯甲烷溶液下放射光譜位置在492-500 nm，以錯合物3呈現青綠色的放光現象最為明顯。在螢光強度定量性質的部份，錯合物1-3及5-7量子產率約為0.020-0.118。在環酯類開環聚合反應方面，鋁錯合物4及11皆展現良好的催化效果以及極佳的分子量分佈度；另一方面，可觀察到含TMClBTP-配位基之鎂錯合物12或鋁錯合物15對左旋乳酸交酯之開環聚合反應具有高度活性。再者，鈦烷氧基錯合物的催化反應，則以單取代雙核鈦錯合物18表現最為傑出。由動力學之研究顯示，起始劑15對於左旋乳酸交酯進行催化反應，單體濃度對於左旋乳酸交酯之開環聚合反應為一級反應；另一方面，鈦錯合物18與單體濃度對於環己內酯之開環聚合反應皆為一級反應，更可以說明其“配位-插入”的開環聚合反應機構。此外，錯合物17搭配n-Bu4NBr對二氧化碳/環氧丙烷進行偶合反應，呈現出具有高生產率(TON = 1160)及良好的催化活性(TOF：120 h-1)。而新穎含胺基側臂架橋之雙BTP配位基的三核鎂金屬錯合物22為一雙效催化劑，在環己內酯開環聚合反應方面，不僅具有“living”也擁有“immortal”性質。另外，錯合物22對二氧化碳/環氧環己烷(cyclohexene oxide, CHO)在外加助催化劑銨鹽(n-Bu4NBr)下進行偶合反應產生其碳酸環己烯酯(cyclohexene carbonate, CHC)，為cis-CHC。另一方面，錯合物24-26無論是進行CO2/CHO的偶合或共聚合反應，皆有良好的催化活性。三核鈷金屬錯合物25是三種催化劑中反應效果最為優異的，在共聚合反應方面，不僅有良好的控制性和催化活性(Mn = 10100, PDI = 1.39)，並且在外加n-Bu4NCl下對CO2/CHO進行偶合反應，呈現出具有高生產率(TON = 990)及優異的反應性(TOF = 495 h-1)。

關鍵字

苯並三唑苯酚氧基 ； 開環聚合 ； 二氧化碳/環氧化物偶合和共聚合反應

並列摘要

Several novel metal complexes bearing BTP ligands (BTP = N,O-bidentate benzotriazole phenoxide), [{(-C1BTP)AlMe2}2] (1), [(C1BTP)2AlMe] (2), [(C1BTP)3Al] (3), [(C1BTP)2Al(OAn)] (4), [{(C1BTP)2Al}2(-O)] (5), [{(C1BTP)2Al(-OH)}2] (6), [(C1BTP)Al2Me5] (7), [(CMe2PhBTP)AlMe2] (8), [(t-BuBTP)AlMe2] (9), [(CMe2PhBTP)2AlMe] (10), [{(CMe2PhBTP)2Al}2(-O)] (11), [(TMClBTP)2Mg(THF)2] (12), [(CMe2PhBTP)2Al(NMe2)] (13), [(t-BuBTP)2Al(NMe2)] (14), [(TMClBTP)2Al(NMe2)] (15), [{(t-BuBTP)2Al}2(-O)] (16), [{(TMClBTP)2Al}2(-O)] (17), [(-C8BTP)Ti(OiPr)3]2 (18), [(C8BTP)2Ti(OiPr)2] (19), [(t-BuBTP)2Ti(OiPr)2] (20), [(TMClBTP)2Ti(OiPr)2] (21) and trimetallic complexes incorporated by amine-bis(benzotriazole phenolate) ligands, [(C1NNBiBTP)2Mg3(OBn)2] (22), [(C1PPBiBTP)2Mg3(OBn)2] (23), [(C1NNBiBTP)2Zn3(OAc)2] (24), [(C1NNBiBTP)2Co3(OAc)2] (25) and [(C1NNBiBTP)2Ni3(OAc)2(H2O)2] (26) were synthesized and structurally characterized. Their optical properties and catalytic activities in ring-opening polymerization (ROP) of lactone and carbon dioxide/epoxides coupling and copolymerization were systematic studied. Luminescent properties of complexes 1-3 and 5-7 in solution were studied, and it was found that the maxima emission wavelength (max) of 1-3 and 5-7 is in the range 492 to 500 nm and the quantum yield is 0.020-0.118, depending on the BTP ligands coordinating to the metal center. Experimental results demonstrated that complexes 4, 11/(9-anthracenemethanol (9-AnOH)), 12/9-AnOH, 15, 18 and 19 efficiently catalyze the ring-opening polymerization of -caprolactone (-CL) or/and L-lactide (L-LA) in a controlled fashion, yielding polymer with the expected molecular weights and narrow polydispersity indices (PDIs). Single-site Al amide 15 is an efficient initiator for the LA polymerizations with a living character, and the polymerization displays a first-order dependence on the L-LA concentration. Kinetic studies of ε-CL polymerization initiated by 18 were investigated using in situ 1H NMR spectroscopy; the polymerization exhibited first-order dependence on both complex 18 and ε-CL concentrations. Additionally, bimetallic BTP-ligated alumoxane 17 is an active catalyst (TOF: 120 h-1) for the coupling of CO2 with PO in the presence of n-Bu4NBr to give propylene carbonate under mild conditions. New trimetallic magnesium complexes bearing amine-bis (benzotriazole phenolate) were synthesized for bifunctional catalysis. Complex 22 catalysed -CL polymerizations in not only a ‘living’ manner but also in an ‘immortal’ fashion. Additionally, tri-Mg 22 was active for the coupling of CO2 with cyclohexene oxide (CHO) on addition of n-Bu4NBr co-catalysts to give cis-cyclohexene carbonate under mild conditions. A novel tri-Co 25 catalyst for the copolymerization of CHO and CO2 in controlled manner, yielding poly(cyclohexene carbonate) with the highly molecular weights and narrow PDIs (Mn = 10100, PDI = 1.39). The 25/n-Bu4NCl catalytic system shows good productivity (TON: 990) and activity (TOF: 495 h-1) under optimal conditions.

並列關鍵字

Copolymerization ； Carbon Dioxide/Epoxides Coupling ； Ring-Opening Polymerization ； Benzotriazole Phenoxide

參考文獻

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