含2-胺基-4,6-二甲基嘧啶之配位基與過渡金屬鹵化物之合成及結構鑑定

Synthesis and structures of transition metal halide complexes containing 2-Amino-4,6-dimethylpyrimidine ligand

蔡嘉慶(Chia-Ching Tsai)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2009年)

https://doi.org/10.6840/cycu200900978

摘要

本論文主要探討含2-胺基-4,6-二甲基嘧啶配位基分別和一價銅 與二價鋅金屬鹽類化合物的化學。
以一價鹵化銅金屬鹽類與2-胺基-4,6-二甲基嘧啶(L)分別在氯化氫水溶液、溴化氫水溶液與氯化氫甲醇水溶液下反應，得到化合物Cu4Cl6(HL)2 , 1，[Cu4Br6][HL]2 , 2與[Cu Cl3][H2L] , 3，另外氯化鋅與L在氯化氫甲醇水溶液下反應，得到化合物[ZnCl4][HL] 2．H2O , 4。
化合物 1 是一個四核銅的單元結構，鍵結了兩個L配位基嘧啶上的氮端原子，在分子間配位基質子化的Npm-H---Cl與氨基Nam-H---Cl氫鍵作用下，使化合物 1 形成一維氫鍵的超分子。化合物 2由銅原子與溴原子之[Cu4Br6]2-金屬無機層形成帶狀結構，而此無機帶狀結構與配位基利用各種氫鍵作用力形成超分子。化合物 3 中藉由各分子間Npm-H---Cl、Nam-H---Cl、Cpm-H---Cl及C-H---Cl氫鍵作用力，利用CuCl3與配位基形成二維氫鍵層狀結構。化合物 4 中具有ZnCl4陰離子與配位基之間Npm-H---Cl、Nam-H---Cl、C-H---Cl、Npm-H---O及自於水分子的O-H---Cl氫鍵；並且在配位基芳香環之間存在著π鍵作用力。

關鍵字

氫鍵 ； 銅

並列摘要

The reactions of the polydentate ligand 2-amino-4,6-dimethyl-
pyrimidine (L) with CuX ( X = Cl , Br ) and ZnCl2 afforded the following complexes: Cu4Cl6(HL)2, 1, [Cu4Br6][HL]2, 2, [Cu Cl3][H2L] , 3, and [ZnCl4][HL] 2．H2O , 4. All the complexes have been structurally characterized by X-ray crystallography.
In the new tetranuclear complex Cu4Cl6(HL)2 , 1, with uncommon square Cu(I) tetramers of mixed Td-Tp-Td-Tp geometries, the Cu(I) atoms are bridged and bonded by six chloride atoms and two mono-protonated, HL+, ligands. The molecules in 1 are interlinked through N-H---Cl hydrogen bonds to form 3-D supramolecular structures. In complex [Cu4Br6][HL]2 , 2, the μ4- and μ2- bromide atoms of the mono-protonated, HL+, ligands interact with the 1-D Cu4Br6 inorganic chains through C-H---Br and N-H---Br hydrogen bonds. The cations and anions in 2 are interlinked through C-H---Br, N-H---Br and N-H---N hydrogen bonds to form a 3-D hydrogen-bounded structure. Complex [CuCl3][H2L], 3 shows 2-D layer formed by bis-protonated H2L2+ ligands and CuCl32- anions which are interlinked through N-H---Cl and C-H---Cl hydrogen bonds. The structure of [ZnCl4][HL]2．H2O, 4, consists a tetrahedral ZnCl42- anion, two mono-protonated HL+ ligands and one water molecule. Their molecules are interlinked through N-H---Cl, C-H---Cl, O-H---Cl hydrogen bonds and π – π stackings.

並列關鍵字

copper ； hydrogen bond

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