含有吡啶不對稱二亞胺銅化合物合成及活性探討

Synthesis and Reactivity Study of Asymmetrical β-Diketiminato Copper Complexes Bearing a Pendant Pyridine Group

郭振宇(Chen-Yu Kuo)

指導教授 ： 許智能

高雄醫學大學/生命科學院/醫藥暨應用化學研究所/碩士(2013年)

https://doi.org/10.6832/KMU.2013.00103

摘要

近幾十年來二亞胺 (β-diketimine) 配位基的研究愈來愈熱門，主要是因為二亞胺配位基易形成較擁擠的配位環境，可用來穩定銅(I)金屬中心形成不飽和的配位環境。在二亞胺配位基的研究中，大部分著重在氮原子上以芳香環取代基為主。在本論文中利用具有不對稱三芽基的二亞胺配位基 (分別含有芳香環取代基及脂肪族取代基)銅(I)羰基化合物，探討其在電子特性以及供電子能力上與對稱的二亞胺配位基的差異性。因此，這類化合物的反應性研究就是本論文的重點。藉由X-ray繞射可以發現，銅(I)三苯基膦的加成物是吡啶手臂盪開的三配位形式，可以推測銅(I)羰基化合物應有相似的鍵結模式。本論文所合成的銅(I)羰基及銅(I)三苯基膦加成物皆由光譜鑑定來確認分子結構。

關鍵字

二亞胺配位基

並列摘要

The β-diketiminato ligands have been gaining much interest over the past several decades because they can act as sterically crowded spectator ligands to stabilize copper(I) metal center for bio-mimetic mode studies of copper containing enzymes. Most of β-diketiminato ligands are designed to have a symmetric N-aryl or N-alkyl substituted groups due to their clean and simple synthetic procedures. Therefore, the synthesis of asymmetrical N-aryl-N’-alkyl β-diketiminato copper(I) carbonyl complexes will help us understand the electronic properties of the new ligands and offer comparison on the electronic donating property of its symmetric N-aryl or N-alkyl counter part. For this reason, the reactivity study of asymmetry tridenate N,N’-substituted β-diketiminato copper (I) complexes were examed. The X-ray crystallographic studies of copper(I) triphenylphosphine adduct showed a tridentate coordination mode with a dangling pyridyl arm this indicates the copper(I) carbonyl adducts may have the similar structure. All copper(I) complexes were characterized by routine spectroscopy.

並列關鍵字

β-Diketiminato

參考文獻

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