配位基N, N’−二(6–甲基−2−吡啶)甲咪和銅金屬化合物之研究

Chemistry of Copper metal complexes containing N,N’-di(6-methyl-2-pyridyl)formamidine ligand

李智偉(Chih-Wei Lee)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2002年)

https://doi.org/10.6840/cycu200200119

摘要

本篇論文主要討論含配位基N,N’−二(6 –甲基−2−吡啶)甲咪與銅一價和銅二價化合物的化學。

將N,N’−二(6 –甲基−2−吡啶)甲咪簡稱為HDMepyF與鹵素銅化合物反應而得到含新的鍵結模式的化合物。所有產物的結構均由單晶X-ray解析出。化合物CuCl2(HDMepyF)，1的晶系為 orthorhombic，空間群為Pca21，a = 18.240 (2)，b = 11.2424 (11)，c = 7.3078 (11) Å，體積為1498.5(3) Å3，單位晶格內含4個分子，R1 = 0.0450和wR2 = 0.0883。化合物Cu2Cl4(HDMepyF)2 ∙ 2 CH2Cl2， 2 ∙ 2 CH2Cl2的空間群為P ，晶系為triclinic，a = 9.216 (3)，b = 10.1744 (17)，c = 10.898 (3) Å， = 87.66 (2)， = 66.83 (2)， = 82.09 (2)o，單位晶格內含1個分子，體積為930.4(4) Å3，R1 = 0.0482和wR2 = 0.1311。化合物Cu2Br4(HDMepyF)2 ∙ 0.5 THF，3 • 0.5 THF的晶系為triclinic，空間群為P ，a = 10.1760 (15)，b = 13.4020 (19)，c = 13.484 (2) Å， = 89.822 (10)， = 75.274 (12)， = 72.956 (10)o，體積為1695.3(5) Å3，單位晶格內含2個分子，R1 = 0.0576和wR2 = 0.1214。化合物Cu4I4(HDMepyF)2，4的晶系為triclinic，空間群為P ，a = 7.6842 (9)，b = 10.0563 (13)，c = 12.1503 (13) Å， = 104.734 (9)， = 91.390 (7)， = 109.217 (8)o，體積為851.42(17) Å3，單位晶格內含1個分子，R1 = 0.0289和wR2 = 0.0728。化合物Cu2(HDMepyF)2[PF6]2 ∙ CH2Cl2，5 ∙ CH2Cl2的晶系為monoclinic，空間群為Cc，a = 23.0154 (15)，b = 11.9167 (8)，c = 15.4577 (10) Å， = 118.1990 (10)，體積為3736.4(4) Å3，單位晶格內含4個分子，R1 = 0.0383和wR2 = 0.1021。化合物Cu2(DMepyF)2，6的晶系為monoclinic，空間群為C2/c，a = 26.937 (7)，b = 4.4631 (12)，c = 23.963 (6) Å， = 121.245 (4)，體積為2463.1(11) Å3，單位晶格內含4個分子，R1 = 0.0387和wR2 = 0.0495。化合物1結構為四面體，化合物中心銅原子被兩個氯原子與配位基HDMepyF上的兩個氮原子鍵結。化合物2和3都是雙核的化合物，化合物中心的兩個銅原子分別被兩個鹵素原子所橋接。每個銅原子也被單一的鹵素原子鍵結並且被配位基HDMepyF螯合而形成扭曲的四角錐構型。化合物4是一個四核的化合物，四個銅都在同一個平面上；每個銅都是三配位。其中相鄰的兩個銅原子分別被一個碘原子和一個配位基HDMepyF橋接。銅原子之間的距離為2.605(1)和2.678(1) Å。在化合物1−4，均為中性的配位基以胺基和相鄰的吡啶上的氮原子鍵結到中心銅原子。化合物5、6都是雙核化合物。化合物5中配位基HDMepyF以一個新的鍵結型式鍵結到銅原子，形成螯合和橋接的鍵結模式。化合物5因配位基受拘束而有成對掌性。兩個銅原子都是三配位。每個銅原子在化合物5中處於高度不對稱的環境，分子內銅原子之間的距離為2.803(1) Å。在化合物6中，兩個銅原子被兩個陰離子的DMepyF−配位基橋接而形成雙核化合物，銅原子間的距離為2.5463(9) Å。銅原子在化合物6中的鍵結模式趨近於直線型。

關鍵字

銅銅金屬間距 ； 幾何構形 ； 銅化學

並列摘要

This thesis discusses the chemistry of copper(I) and copper(II) complexes containing N,N’-di(6-methyl-2-pyridyl)formamidine (HDMepyF).

The reactions of N, N’-di(6-methyl-2-pyridyl)formamidine (HDMepyF) or its anion with copper halide produced complexes with new coordination fashions. All complexes were characterized by X-ray crystallography. Complex CuCl2(HDMepyF), 1, is orthorhombic, space group Pca21, with a = 18.240 (2), b = 11.2424 (11), c = 7.3078 (11) Å, V = 1498.5(3) Å3, and Z = 4, with final residuals R1 = 0.0450 and wR2 = 0.0883. Complex Cu2Cl4(HDMepyF)2 ∙ 2 CH2Cl2, 2 ∙ 2 CH2Cl2, is triclinic, space group P , with a = 9.216 (3), b = 10.1744 (17), c = 10.898 (3) Å, = 87.66 (2), = 66.83 (2), = 82.09 (2)o, V = 930.4(4) Å3, and Z = 1, with final residuals R1 = 0.0482 and wR2 = 0.1311. Complex Cu2Br4(HDMepyF)2 ∙ 0.5 THF, 3 • 0.5 THF, is triclinic, space group P , with a = 10.1760 (15), b = 13.4020 (19), c = 13.484 (2) Å, = 89.822 (10), = 75.274 (12), = 72.956 (10)o, V = 1695.3(5) Å3, and Z = 2, with final residuals R1 = 0.0576 and wR2 = 0.1214. Complex Cu4I4(HDMepyF)2, 4, is triclinic, space group P , with a = 7.6842 (9), b = 10.0563 (13), c = 12.1503 (13) Å, = 104.734 (9), = 91.390 (7), = 109.217 (8)o, V = 851.42(17) Å3, and Z = 1, with final residuals R1 = 0.0289 and wR2 = 0.0728. Complex Cu2(HDMepyF)2[PF6]2 ∙ CH2Cl2, 5 ∙ CH2Cl2, is monoclinic, space group Cc, with a = 23.0154 (15), b = 11.9167 (8), c = 15.4577 (10) Å, = 118.1990 (10), V = 3736.4(4) Å3, and Z = 4, with final residuals R1 = 0.0383 and wR2 = 0.1021. Complex Cu2(DMepyF)2, 6, is monoclinic, space group C2/c, with a = 26.937 (7), b = 4.4631 (12), c = 23.963 (6) Å, = 121.245 (4), V = 2463.1(11) Å3, and Z = 4, with final residuals R1 = 0.0387 and wR2 = 0.0495. The structure of 1 is tetrahedral in which the Cu(II) center is coordinated by two nitrogen atoms of the HDMepyF ligand and two chloride ligands. Complexes 2 and 3 are dinuclear complexes in which the two Cu(II) centers are bridged by two halide atoms. Each Cu(II) metal center are also coordinated by one terminal halide atom and chelated by one HDMepyF ligand, forming a distorted square-pyramidal geometry. Complex 4 is tetranuclear, in which the four Cu(I) atoms are coplanar; each Cu atom being in a three-coordination environment. Two adjacent copper atoms are bridged by one iodo atom and one HDMepyF ligand. The Cu ∙∙∙ Cu separations are 2.605(1) and 2.678(1) Å. In complexes 1 – 4, the neutral HDMepyF ligands coordinate to the metal centers through one amine nitrogen atom and one adjacent pyridine nitrogen atom. Complexes 5 and 6 are dinuclear complexes. The HDMepyF ligands in complex 5 coordinates to the Cu(I) ions in a new tridentate fashion, forming a chelating and a bridging bonding modes. The molecules are chiral due to the ligand constraints. The two copper atoms are in three-coordination environments and the geometry at copper atoms is severely flattened. Each copper atom of 5 is bound in a highly asymmetric environment, with an intramolecular copper−copper separation of 2.803(1) Å. In complexe 6, two Cu atoms are bridged by two DMepyF- ligands to give a binuclear structure, in which the Cu ∙∙∙ Cu separation is 2.5463(9) Å. The geometries of the copper atoms of 6 are linear.

並列關鍵字

geometries ； Copper complexs ； distances of copper copper separation

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