含有吡啶與二異丙基苯之二亞胺銅化合物合成及活性探討

Synthesis and Reactivity Study of β-Diketiminato Copper Complexes Bearing a Pyridine and Diisopropyl Benzene Substituent Group

盧毓秀(Yuh-Hisu Lu)

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(2012年)

https://doi.org/10.6832/KMU.2012.00129

摘要

近幾十年來二亞胺 (??-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，可用來穩定金屬中心稀有的氧化態和不飽合的配位環境。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) 銅一價化合物，探討兩者不同的反應性，結果發現當二亞胺銅一價化合物配位基上氮旁吡啶的碳鏈長短確實會影響反應性。並且將兩者與異氰基 (CNR) 取代基反應，利用紅外線光譜測定，藉此討論不對稱三芽基的二亞胺配位基的電子特性與對稱的芳香環取代基較為相似，且上述化合物皆成功得到X-ray單晶繞射結構。

關鍵字

二亞胺 ； 銅

並列摘要

The N,N’-substituted β-diketiminato ligands can act as a sterically crowded spectator ligand to stabilize transition metal center and have been gaining much interest over the past several decades. Most of β-diketiminato ligands are designed to have an N-Ar-substituted group due to their clean and simple synthesis procedure as well as their application in the biomimetic system. Except aryl substituents, there were a few copper complexes carried β-diketiminato ligand with alkyl substituents on nitrogen, which were reported by Schaper. To consider the electron donor properties difference between N, N’-aryl and N, N’-alkyl-substituted β-diketiminato ligands, several isocyanide copper(I) adducts were reported by different research groups, separately. However, the electron properties of asymmetrical N-aryl-N’-alkyl β-diketiminato ligand still remain unknown. Therefore, a new type asymmetry tridenate N,N’-substituted β-diketiminato ligand sets (one aryl and one alkyl substituted) were synthesized herein. The isocyanide (CNR) stretching of the asymmetry β-diketiminato copper(I) adducts shows their electronic property of metal center is similar to N, N’-aryl-substituted analogs. All copper(I) complexes were characterized by routine spectroscopy and X-ray crystallography to confirm their formula and stucture.

並列關鍵字

β-Diketiminato ； copper

參考文獻

1. Roat-Malone, R. M., Bioinorganic Chemistry. John Wiley & Sons, Inc.: Hoboken, New Jersey, 2002.

2. N. P. Johnson et al., J. Am. Chem. Soc 1985, 107, 6376.

3. Cowan, J. A., Inorganic Biochemistry, An Introduction, 2nd ed. Wiley-VCH: New York, 1997.

4. Huang, H.; Zhu, L.; Reid, B. R.; Drobny, G. P.; Hopkins, P. B., Science 1995, 270, 1842-1845.

5. Su, C. C.; Wu, C. Y., Chemistry(The Chinese Chem. Soc., Taipei) 1996, 54, 57-68.