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

邱佳儷(Chia-Li Chiou)

指導教授 ： 陳竹亭

國立臺灣大學/理學院/化學研究所/碩士(2005年)

https://doi.org/10.6342/NTU.2005.00137

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。

關鍵字

苯胺亞胺 ； 鈀金屬 ； 聚合

並列摘要

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.

並列關鍵字

anilido-imine ； palladium complexes ； polymerization

參考文獻

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