新穎含胺基雙苯並三唑苯酚氧基之金屬錯合物合成結構鑑定、光性質分析以及應用於環酯類開環聚合反應與二氧化碳/環氧化物偶合反應

新穎含雙苯並三唑苯酚氧基(C1PPBiBTP2-, C1NNBiBTP2-)之配位基已成功地由Mannich反應合成，利用2-(2H-benzotriazol-2-yl)-4-methylphenol再加上過量的paraformaldehyde與一級胺類反應迴流即可獲得胺基雙苯並三唑苯酚氧基(amineBiBTP-H2)。新型配位基(C1PPBiBTP-H2)可與醋酸銅(Cu(OAc)2‧H2O)進行反應，然後再進一步與 4-dimethylaminopyridine, 4-picoline, 4-tertbutylpyridine, 1-methylimidazole等四種共配位基進行反應，成功地合成出一系列五配位之銅金屬錯合物(1)-(5)。再者，此兩種配位基(C1PPBiBTP-H2, C1NNBiBTP-H2)也可與鈦、鋯、鉿金屬進行反應，形成有氧做架橋之雙金屬錯合物或單核金屬錯合物。並藉由X-ray單晶繞射儀與元素分析儀鑑定十個金屬錯合物之結構及純度。此外，利用UV-Vis光譜儀測得五個銅金屬錯合物之紫外光區吸收波長介於270nm至290nm之間，莫耳吸收係數約2.71至5.01×104 (M-1cm-1)。而d-d transition的可見光區吸收，其最大波長介於686nm至760nm之間，莫耳吸收係數約165至228 (M-1cm-1)之間。應用於催化二氧化碳/環氧化物的偶合反應方面，由實驗結果顯示，銅錯合物(1)在最佳條件下(150psi, 50℃)反應9小時，轉換率可達95%，呈現出高生產率(TON=3800)及優異的反應性(TOF=422 h-1)。另外在鈦、鋯和鉿金屬錯合物(6)-(10)的催化應用，對於環酯類開環聚合反應及二氧化碳/環氧化物共聚合反應，皆以雙鋯金屬錯合物(9)表現最為顯著。在左旋乳酸交酯開環聚合反應中，不僅具有“living”也擁有“immortal”的性質。也有對外消旋乳酸交酯進行立體選擇性的探討，聚合狀態傾向於isotatic的排列方式，Pm值為0.70。最後在對於二氧化碳/環氧環己烷 (cyclohexene oxide, CHO)的共聚合反應方面，在100℃、500psi，並無外加任何助催化劑條件之下，可成功合成出聚碳酸酯共聚合物，顯現出此一雙金屬錯合物對環酯類開環聚合反應及二氧化碳/環氧化物共聚合反應皆有不錯的催化活性與控制性。

關鍵字

二氧化碳/還氧化物偶和反應；二氧化碳/還氧化物共聚合反應；開環聚合反應

並列摘要

A novel amino-bis(benzotriazole phenoxide) ligand (amineBiBTP-H2), C1PPBiBTP-H2 and C1NNBiBTP-H2 was prepared from the Mannich condensation of 2-(2H-benzotriazole-2-yl)-4-methylphenol with the mixtures of excess paraformaldehyde and primary amine under reflux conditions. The reaction of C1PPBiBTP-H2 with copper acetate in the absence or in the presence of four kinds of neutral co-ligand (4-dimethylaminopyridine, 4-picoline, 4-tertbutylpyridine, 1-methylimidazole). Also, amineBiBTP-H2 reacted with Titanium, Zirconium and Hafnium becoming dimer complexes with an oxygen as bridge in the between or a moomer complexes with two coordinated isopropoxide. A series of monomer five-coordinated copper complexes and Ti, Zr, Hf complexes have been successfully synthesized and structurally characterized by single crystal X-ray diffraction as well as microanalysis. The optical properties and catalysis for epoxides with carbon dioxide coupling reaction of copper complexes 1-5 were studied. The UV absorption wavelength of complexes 1-5 are ranging from 270-279 nm in solution. For their visible absorption, the maximum absorption wavelength (max) of d-d transition was observed in the range from 686 to 760 nm. Experimental results indicated that complex 1 is an active catalyst (TOF=120 h-1) for the coupling reaction of propylene oxide with carbon dioxide under mild conditions. For Ti, Zr, Hf metal complexes, Zr complex showed the best catalysis activity no matter for ring-opening polymerization of cyclic ester or copolymerization of cyclohexene oxide with carbon dioxide. There is not only in a ‘living’ manner with the expected molecular weights and narrow molecular weight distribution but also in an ‘immortal’ fashion for ring-opening polymerization of L-lactide (L-LA). Furthermore, Zr complex catalyzed rac-LA to yield heterotatic PLA (Pr=0.70). Finally, the copolymerization of cyclohexene oxide with carbon dioxide in the absence of co-catalyst to give poly(cyclohexene carbonate) under 100℃ and 500 psi. From above experiments reveal that Zr complexe is a bifunctional catalyst with excellent activity.

並列關鍵字

Ring-Opening Polymerization ； CO2/Epoxides Coupling reaction ； CO2/Epoxide Copolymerization

參考文獻

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新穎含胺基雙苯並三唑苯酚氧基之金屬錯合物合成結構鑑定、光性質分析以及應用於環酯類開環聚合反應與二氧化碳/環氧化物偶合反應

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