利用新型不對稱五氮配基合成雙核鎳金屬錯合物與結構分析

Synthesis, Structural Characterization of Dinuclear metal complex,[Ni2L2](H2L = N-(6-(1,8-naphthyridin-7-ylamino)pyridin-2-yl)acetamide)

蔡傑峰(Chieh Feng Tsai)

指導教授 ： 彭旭明

國立臺灣大學/理學院/化學研究所/碩士(2017年)

https://doi.org/10.6342/NTU201700371

摘要

利用新型不對稱五核配基N-(6-(1,8-naphthyridin-7-ylamino)
pyridin-2-yl) acetamide合成金屬簇錯合物與結構分析、電化學性質、結構穩定性等特性探討。
此新型不對稱配基可由S. L. Buchwald所提出的鈀金屬鹽類催化反應而得到，並經由NMR、FAB質譜鑑定證實得到產物。將合成出的配基與Ni(OAc)2 ∙ 4H2O金屬鹽類於高溫萘燒下反應產物經由DCM萃取後以擴散法結晶而得,X-ray單晶繞射解析其錯合物為單斜晶系，空間群為P21/c，與實驗室傳統五核金屬串不同的是，其主體結構是由兩個Ni2+與兩個配基以彎曲螯合的方式配位，在其配位環境中，Ni2+皆為四配位的square planar，與一配基上的一個萘啶、一個吡啶上的氮原子及醯胺上的氧原子進行配位，另外亦與另一個配基上的萘啶氮原子進行配位，結構中兩個配基與兩個鎳相互鍵結形成一金屬錯合物，其金屬間距離為2.7635(4) Å，並參照結構類似的文獻，以金屬間鍵長推測，此一金屬錯合物間並沒有金屬金屬鍵。另外從錯合物的紅外線光譜中並沒有看到N-H的吸收峰，由此可以得知配基在此一結構中是有完全解離的。並使用熱重分析儀測量其結構穩定性可至294.46 °C。在電化學CV測量圖中顯示化合物中並沒有氧化還原電子對。並在磁性測量結果中，其化合物磁性圖顯示為逆磁性，與推論相符合。

關鍵字

金屬錯合物

並列摘要

The aim of this research is to study the synthesis, structure and properties of the dinuclear nickel complexes which the ligand is N-(6-(1,8-naphthyridin-7-ylamino)pyridin-2-yl) acetamide.
The novel asymmetrical ligand was synthesized by palladium-catalyzed reaction which was proposed by S. L. Buchwald , and the product was characterized by NMR and FAB-MS. First of all, we reacted this ligand with Ni(OAc)2∙ 4H2O at high temperature of melt naphthalene, we successfully obtaines one dinuclear compound, [Ni2L2].
The X-ray structure studies of [Ni2L2] reveals the crystal system is monoclinic and space group is P21/c.
In In this structure the Ni ion is tetra-coordination bonded to one oxygen atoms and 3 nitrogen atoms.
Different to the traditional penta-nuclear ligand, this ligand is bent configuration. Ni1 is bonded to one pyridine N atom, one naphthyridine N atom,one amide O atom and one naphthyridine N atom from another ligand. Two Ni atom chelated by two ligands in formation of metal clusters. The metal to metal distance is 2.7635(4) Å. According to the above literature and nickel valence, we guess there is no bond between nickel to nickel.
The IR spectrum of [Ni2L2] reveals that ligands in this complex was deprotonated. No N-H absorption (3700 – 3300 cm-1) is found in this IR spectrum. The CV of [Ni2L2] complex show no redox electron pair. The TG analysis of [Ni2L2] reveals that weight loss was occurred and thermally stable up to 294.46 °C.The magnetic properties shows that the complex is diamagnetism.

並列關鍵字

metal complex

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