含吡啶不對稱二亞胺銅化合物的螯合或雙聚化研究探討

Chelation or Dimerization on the Asymmetrical β-Diketiminato Copper Complexes Bearing a Pendant Pyridyl Group

曾禹瑄(Yu-Hsuan Tseng)

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.2012.00121

摘要

二亞胺配位基可以扮演一個模擬生物體的配位基，與銅離子形成鍵結後可以執行模擬生物體的化學反應，像是金屬酶。在本論文中合成新型不對稱二亞胺配位基，旁邊具有一個吡啶取代基 (HL3, HL4)，可以發展出一系列新的模擬生物體的銅化合物的模型。不對稱二亞胺的鋰(I) (LiL3 (2), LiL4 (3)) 化合物和銅(I) (CuL3 (4), Cu2(??-L4)2 (5)) 化合物被合成出且藉由光譜與X-ray單晶繞射鑑定。根據單晶結構分析可發現含有吡啶取代基的二亞胺配位基鋰(I)化合物和銅(I)化合物的幾何結構可分成螯合或雙聚化的鍵結模式。含有吡啶取代基的二亞胺鋰(I)化合物與銅(I)化合物皆展示出螯合與雙聚化的鍵結模式。在路易士鹼存在的情況下，含有吡啶取代基的銅化合物會去螯合或去橋接而形成異氰基化合物 (L3CuCN(C6Me2H3) (6), L4CuCN(C6Me2H3) (7), (L3Cu)2-μ-(C2N2C6H4) (8), (L4Cu)2-μ-(C2N2C6H4) (9))。而這些異氰基化合物皆有利用NMR光譜和X-ray單晶繞射來鑑定。

關鍵字

不對稱二亞胺銅化合物 ； 銅異氰基化合物 ； 螯合 ； 雙聚化

並列摘要

The N,N’-aryl β-diketiminato ligands can act as a biomimetic ligand to bind copper ion and perform chemical biomimetic reaction such as a metalloenzymes does. We report herein a series of new type asymmetry tridenate N-aryl-N’-alkyl β-diketiminato ligand sets bearing a pendant pyridyl group (HL3, HL4) to develop new class of biomimetic copper complex model. The asymmetry β-diketiminato lithium(I) (LiL3 (2), LiL4 (3)) and copper(I) complexes (CuL3 (4), Cu2L42 (5)) were prepared and characterized by spectroscopic and X-ray crystallography. According to the crystallographic analysis, the geometry of lithium(I) and copper(I) complexes containing an asymmetry β-diketiminato ligand could divide by chelation or dimerization binding modes. The pyridyl arm of β-diketiminato may exhibit chelated or bridged bonding mode in both lithium(I) and copper(I) complexes. In presence of Lewis bases of 2,6-dimethylphenyl isocyanide {CN(C6Me2H3)} and para-diisocyanide benzene {(C2N2C6H4)}, the pyridyl arm of copper(I) complexes will de-chelated or de-bridged to form the isocyanide adduts. These isocyanide adduts (L3CuCN(C6Me2H3) (6), L4CuCN(C6Me2H3) (7), (L3Cu)2-μ-(C2N2C6H4) (8), (L4Cu)2-μ-(C2N2C6H4) (9)) have been characterized by NMR spectra and X-ray diffraction.

並列關鍵字

Asymmetrical β-Diketiminato Copper Complexes ； Copper isocyanide adduts ； Chelation ； Dimerization

參考文獻

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