含胺基苯並三唑苯酚氧基之新穎銅與鈀金屬錯合物合成、結構鑑定及催化應用

Synthesis, characterization and catalysis of novel copper and palladium complexes bearing amino-benzotriazole phenoxide ligands

李司元(Ssu-Yuan Li)

指導教授 ： 柯寶燦

中原大學/理學院/化學研究所/碩士(2012年)

https://doi.org/10.6840/cycu201200088

摘要

本論文已成功合成一系列含胺基苯並三唑苯酚氧基 (amino-benzotriazole phenoxide，BTP)銅與鈀金屬錯合物[(C1DEABTP)Cu(bipy)]ClO4 (1)、[(C8DEABTP)Cu(bipy)]ClO4 (2)、[C8DBABTP]2Cu (3)與[C8DBABTP] 2Pd (4)，並利用X-ray單晶繞射儀與元素分析儀鑑定三個銅及一個鈀金屬錯合物證明其結構。並藉由UV/Vis光譜儀測得三個銅金屬錯合物之紫外光區吸收波長介於299 nm與307 nm之間，顯示配位基內有*的轉移。由比爾定律計算出最大吸收波長的莫爾吸收係數約為22100 M-1cm-1至34820 M-1cm-1。另外，在可見光區吸收波長介於745 nm與753 nm處可測得銅錯合物的d-d躍遷之吸收，莫爾吸收係數約為129 M-1cm-1與157 M-1cm-1。
四配位的鈀金屬錯合物[(C8DBABTP)2Pd] (4)，可進行鈴木偶合反應催化應用， 由實驗結果顯示錯合物(4)具有優異的催化活性，可以在半小時內即可使反應達到平衡，且產率高達98.4 %；與原觸媒系統相比轉化率及產率皆有顯著的提升。

關鍵字

乳酸交酯 ； 開環聚合反應 ； 鈀金屬 ； 銅金屬

並列摘要

A series of amino-benzotriazole phenol ligands, (alkyl = CH3, C1DEABTP-H
(A), alkyl = C8H17, C8DEABTP-H(B) and C8DBABTP-H(C)) were prepared through the Mannich condensation of 4-alkyl-2-(2H-benzotriazol-2-yl)phenol with the mixtures of excess paraformaldehyde and secondary amine under reflux conditions. Copper and palladium complexes (1-4) supported by amino-benzotriazole phenoxide ligands were synthesized and fully characterized.
According to spectroscopic studies of UV-Vis in complexes 1-3. Their UV absorption wavelengths are in the range of 299 nm and 307 nm with molar absorption coefficient of 22100 to 34820 M-1cm-1 . For their visible absorptions, the maximum absorption wavelengths (λmax) of d-d transition were observed in the range from 745 to 753 nm with molar absorption coefficient of 129 to 157 M-1cm-1.
Among them, complex 4 was demonstrated to catalyze Suzuki-Miyaura coupling reaction in comparison with the original catalyst system [Pd(OAc)2/PPh3]. Experimental results showed the 10-(naphthalene-3-yl)-9-phenylanthracene could be efficiently synthesized. In the series of experiment, we found that the [(C8DBABTP)2Pd] (4) is the most efficient catalyst among the palladium complexes.

並列關鍵字

palladium ； lactide ； copper ； ring opening-polymerization

參考文獻

5. O’Keefe, B.; Hillmyer, M. A.; Tolman, W. B. J. Chem. Soc., Dalton Trans. 2001, 2215.

13. Dittrich, W.; Schulz, R. C. Angew. Makromol. Chem. 1971, 15, 109.

14. Kricheldorf, H. R.; Berl, M.; Scharnagl, N. Macromolecules 1988, 21, 286.

17. Chisholm, M. H.; Gallucci, J. C.; Zhen H. Inorg. Chem. 2001, 40, 5051.

20. A. Suzuki, Acc Chem. Res., 1982, 15, 178.