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標題: | 含苯胺亞胺不對稱雙牙配基鈀金屬之結構及反應性的研究 Structure and Reactivity of Palladium Complexes Bearing Asymmetric Anilido-Imine Bidentate Ligands |
作者: | Chia-Li Chiou 邱佳儷 |
指導教授: | 陳竹亭 |
關鍵字: | 苯胺亞胺,鈀金屬,聚合, anilido-imine,palladium complexes,polymerization, |
出版年 : | 2005 |
學位: | 碩士 |
摘要: | 本篇論文報告合成鄰亞胺苯胺衍生物 (o-C6H3R'2)NHC6H4CH=N(o-C6H3R2) ( 2a R' = iPr, R = iPr; 2b R' = CH3, R = iPr; 2c R' = iPr, R = CH3; 2d R' = CH3, R = CH3, 2e R' = CH3, R = H),並利用正丁基鋰脫去苯胺氮上的氫,得到亞胺苯胺陰離子雙牙配基鋰錯合物LiN(o-C6H3R'2)C6H4CH=N(o-C6H3R2) (L, 3a R' = iPr, R = iPr; 3b R' = CH3, R = iPr; 3c R' = iPr, R = CH3; 3d R' = CH3, R = CH3),化合物(3)有明顯的放光性質,特就其光學物理特性與結構的相關性進行探討。
以衍生物(3)與鈀金屬錯合物(COD)Pd(Me)Cl/PPh3反應,可生成平面四邊形錯合物(L)Pd(CH3)PPh3 (4) ,核磁共振光譜顯示甲基選擇亞胺的對位。配基(3) 與烯丙基鈀金屬錯合物[(η3-C3H4R')PdCl]2反應,皆生成兩個烯丙基錯合物幾何異構物(5a R' = CH3; 5d R' = Ph),以二維NMR光譜圖鑑定,烯丙基的取代基位置隨著苯胺亞胺上取代基的變化,可因其立體障礙的不同,造成其異構物比例的改變。 鈀金屬錯合物(L)Pd(CH3)(PPh3) (4)用在Heck催化耦合反應,可有103~104的TON(turn-over-number),對於Sonogashira及Suzuki催化反應亦有相當的活性,可將此催化劑應用在聚冰片烯反應,活性可達約105g PNmol-1h-1。 With recent versatile applications in bioinorganic, main group, and transition metal chemistry, the research in β-diketiminato ligands of N-N bidentates and the salicylaldiminato ligands of N-O bidentates has been rising dramatically. We have successfully synthesized a series of ligands with functional combination of anilido-imine (o-C6H3R'2)NHC6H4CH=N(o-C6H3R2) ( 2a R' = iPr, R = iPr; 2b R' = CH3, R = iPr; 2c R' = iPr, R = CH3; 2d R' = CH3, R = CH3, 2e R' = CH3, R = H) and their related anionic form LiN(o-C6H3R'2)C6H4CH=N(o-C6H3R2) (L3) ( 3a R' = iPr, R = iPr; 3b R' = CH3, R = iPr; 3c R' = iPr, R = CH3; 3d R' = CH3, R = CH3) via deprotonation. The photoluminscence nature of complexes 3 corresponding to their structures has been studied. These coordination of derivates (3) can generate a square-planar complex (L)Pd(CH3)(PPh3)(4) by reacting with (COD)Pd(Me)Cl and PPh3. NMR measurements show that the methyl ligand is trans to the imine. The reactions of L3 with [(η3-C3H4R')PdCl]2 afford two geometric isomers of η3-allyl species which have been well characterized by sophisticated 2D-NMR. The steric and electronic effects of the anilido-imine ligands can influence the regioselectivity as well as the ratio of isomers. The palladium complexes (4) are active to the Heck and Suzuki cross-coupling reactions, and its TON can reach to 103~104. These catalysts (4) also show activity about 105gPNmol-1h-1 to the polymerization of norborene. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/38657 |
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顯示於系所單位: | 化學系 |
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