二價過渡金屬化合物與多芽氮配位基之合成、結構研究

Synthesis, Structures of Transition Metal(Ⅱ) Complexes Containing Polydentate Nitrogen Ligands

蘇昶維(Chang-Wei Shu)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2001年)

https://doi.org/10.6840/cycu200100219

摘要

中文摘要

本論文主要探討含多芽氮配位基與二價過渡金屬化合物鍵結的化學。
第一部份探討多芽氮配位基HDpyF [HDpyF = Bis(2-pyridyl)formamidine]與二價過渡金屬化合物的合成與結構特性。[PdCl2(CH3CN)2]和HDpyF在CH3CN中反應，可得到黃色產物Pd2Cl2(DpyF)2, 3, 此結構已由單晶X-ray解析出。DpyF-配位基配位到Pd原子，形成新型的螯合/橋接的三芽鍵結模式。由於化合物3的配位基受到壓迫導致旋光性的出現。化合物3利用CH3CN/ether養晶可以自然分解出具旋光的化合物D­[Pd2Cl2(DpyF)2] × CH3CN, 4, 並且由CD光譜圖可被證實。將LiDpyF和CuCl 於CH3CN中反應，可製備雙核金屬化合物Cu2(DpyF)4, 5。將MCl2 × 6H2O (M = Mn, Co, Cu)和HDpyF在CH3CN中反應，可製備化合物CoCl2(HDpyF), 6、CuCl2(HDpyF), 7與MnCl2(HDpyF), 8。
第二部份探討多芽氮配位基HDMpyF [HDMpyF = Bis(2-(6-methylpyridyl)formamidine)]與二價過渡金屬化合物的合成與結構特性。將CoCl2 × 6H2O和HDMpyF在CH3CN中反應，可製備化合物CoCl2(HDMpyF), 9。將化合物NiX2 (X = Cl, Br)和HDMpyF分別在CH3CN和THF中反應，可製備化合物NiCl2(HDMpyF)2 × CH3CN, 10與NiBr2(HDMpyF)2 × THF, 11。HDpyF及HDMpyF配位基與這些化合物顯示出不同的鍵結模式。

第三部份探討多芽氮配位基2-ampy (2-ampy = 2-amino -pyridine)與二價過渡金屬化合物的合成與結構特性。將PdCl2(CH3CN)2和2-ampy分別溶於在CH3CN和ether中，利用合成養晶可製備化合物trans-PdCl2(2-ampy)2, 12。化合物12具有一組非直線型的N-H---Pd(Ⅱ)作用力。將MnCl2×6H2O、MnCl2分別與2-ampy在CH2Cl2中反應，可製備化合物[H(2-ampy)][MnCl3(H2O)], 13 and [H(2-ampy)]2 [Mn2Cl6(2-ampy)2], 14。化合物13和14 [MnCl3(H2O)]-與[Mn2Cl6(2-ampy)2]2-單位分子，並透過doubly edge-sharing, 形成直鍊的化合物。此直鍊的化合物並藉由氫鍵[H(2-ampy)]+相互交聯，形成二度空間的平面化合物。化合物14顯示出具有兩個不同的2-ampy配位基，一個直接橋接到Mn原子，另一個透過氫鍵的作用經由Cl原子接橋到Mn原子上。

關鍵字

多芽氮

並列摘要

ABSTRACT

This thesis discusses the chemistry of transition metal(Ⅱ) complexes containing polydentate nitrogeneous ligands.
The first part discusses syntheses and structures of transition metal(Ⅱ) complexes containing HDpyF [HDpyF = Bis(2-pyridyl)forma-midine] ligand. Reaction of [PdCl2(CH3CN)2] with HDpyF in CH3CN afforded a yellow product Pd2Cl2(DpyF)2, 3, which was characterized by X-ray crystallography. The DpyF- ligand coordinates to the Pd atoms in a new tridentate fashion, forming a chelating and a bridging bonding modes. The molecules are chiral due to the ligand constraints. Spontaneous resolution of the racemic product can be achieved by crystallization of the yellow product in CH3CN/ether to giveΔ-Pd2Cl2(DpyF)2, 4, and a CD spectrum can be obtained. The reaction of LiDpyF with CuCl in CH3CN, afforded the dinuclear metal complex Cu2(DpyF)2, 5. Reactions of MCl2×6H2O (M = Mn, Co, Cu) with HDpyF in CH3CN, afforded the complexes CoCl2(HDpyF), 6、CuCl2(HDpyF), 7、MnCl2(HDpyF), 8.
The second part discusses syntheses and structures of transition metal(Ⅱ) complexes containing HDMpyF [HDMpyF = Bis(2-(6-methyl-pyridyl)formamidine)] ligand. The reaction of CoCl×6H2O with HDMpyF in CH3CN, afforded the complex CoCl2(HDMpyF), 9. The reaction of complexes NiX2×6H2O (X = Cl, Br) with HDMpyF in CH3CN and THF, afforded the complexes NiCl2(HDMpyF)2×CH3CN, 10 and NiBr2(HDM pyF)2 ×THF, 11. There complexes show different bonding modes for the HDpyF and HDMpyF ligands .
The third part discusses syntheses and structures of transition metal(Ⅱ) complexes containing 2-ampy (2-ampy = 2-aminopyridine) ligand. The reaction of PdCl2(CH3CN)2 with 2-ampy in CH3CN/ether, afforded the complex trans-PdCl2(2-ampy)2, 12. This complex exhibits a pair of nonlinear N-H---Pd(Ⅱ) interactions. The 2-ampy ligand also has been exploited in preparation of metal(Ⅱ) complexes of the formulae [H(2-ampy)][MnCl3(H2O)], 13, and [H(2-ampy)]2[Mn2Cl6(2-ampy)2], 14,. Each repeating unit of complexes 13 and 14, [MnCl3(H2O)]- and [Mn2Cl6(2-ampy)]2-, respectively, is doubly edge-sharing to form one-dimensional chains which are cross-linked by hydrogen bonding to the [H(2-ampy)]+ cations. In complex 14, two different 2-ampy molecules are observed. One bridges the Mn atoms directly, while the other, through hydrogen bonding interaction, bridges Mn atoms via the chloride atoms.

並列關鍵字

Polydentate Nitrogen Ligands

參考文獻

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