- 學位論文
含尿素配位基與二價金屬化合物之合成與結構之探討
Synthesis and Structures of Divalent Metal Complexes Containing Urea Ligand
摘要
含尿素配位基N,N'-dicyclohexyl-N-isonicotinoylurea (DCIU)和N,N'-dicyclohexyl-N-nicotinoylurea (DCNU)已被合成並與金屬鹽類反應。 以DCIU配位基與二價金屬鈷和銅反應，可得到一系列含尿素配位基的金屬化合物CoBr2(DCIU)2(C2H5OH)2，1；CuCl2(DCIU)2， 2；[Cu(DCIU)4(H2O)](ClO4)2，3；CoI2(DCNU)2，6；{[Cu(DCIU)2(H2O)2] (NO3)2}n，7。此外以DCNU配位基與過渡金屬鹵化物反應可得到CuCl2(DCNU)2，4及CuBr2(DCNU)2，5。化合物 1 - 6 中，中性配位基DCIU及DCNU以單芽方式配位至金屬。而化合物 7 中，配位基DCIU以雙芽方式配位至金屬。 含有未配位的水分子在化合物 1 ，4 及 5 的晶體結構中扮演一個重要的角色，水分子以氫鍵連結含尿素化合物的官能基形成一維的鏈。而化合物 2 於晶體結構中未含有水分子，藉由尿素官能基間的氫鍵作用力形成二維結構。在化合物 3 中，陰離子藉由與CH及OH形成的氫鍵存在於主體形成的洞穴，其結構中有四個DCIU配位基佔據於赤道平面並有一個水分子配位在軸上，且DCIU配位基上的吡啶環配製成風車的型式。於化合物 6 中，由於碘原子的大小造成銅金屬扭曲的四面體構型。化合物 7 中，雙芽配位基DCIU經由羰基的氧原子與吡啶環上的氮原子配位形成新穎的十四圓環的一維高分子鏈。
並列摘要
A series of compounds containing the urea ligands N,N'-dicyclohexyl -N-isonicotinoylurea, DCIU, and N,N'-dicyclohexyl-N-nicotinoylurea, DCNU, have been synthesized, and their structures characterized by single crystal X-ray crystallography. The reactions of DCIU with transition metal salts of Co(II) and Cu(II) afforded CoBr2(DCIU)2(C2H5OH)2, 1, and CuCl2(DCIU)2, 2, and [Cu(DCIU)4(H2O)](ClO4)2, 3, CoI2(DCNU)2, 6, {[Cu(DCIU)2(H2O)2](NO3)2}n, 7, while the reactions of DCNU with transition metal halide complexes afforded CuCl2(DCNU)2, 4, and CuBr2(DCNU)2, 5. The neutral DCIU and DCNU ligands in complexes 1 - 6 are coordinated to the metal centers in monodentate fashions, while the DCIU in complex 7 is coordinated to the metal centers in bidentate fashions. In the crystal structures of 1, 4 and 5, the discrete water molecules play an important role in forming the hydrogen bondings which link the molecules of the complexes to form 1-D chains. There is no water molecule inside the crystal structures of 2, and the extended hydrogen-bonding is generated via a combination of the urea functional groups to from 2-D structure. In complex 3, the anions reside within the central cavity of the host species, held by hydrogen bonds from both CH and OH donors. The four DCIU ligands occupy the equatorial plane, while the water molecule occupies one of the axial sites, and pyridine rings of the DCIU ligands are arranged in a windmill fashion. In the complex 6, the copper metal center adopts a distorted tetrahedral coordination geometry, owing to the size of iodide atom. In complex 7, the bidentate DCIU ligands coordinated to metal via oxygen atoms of carbonyl and nitrogen atoms of pyridyl rings, forming novel 1D polymer chains consisting of fourteen-membered metallocycles.