Synthesis and characterization of nickel(II) complexes containing ligands derived from disaccharides and 1,3-diaminopropane
Synthesis and characterization of nickel(II) complexes containing ligands derived from disaccharides and 1,3-diaminopropane
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含有二糖和 1,3-二氨基丙烷配体的镍 (II) 配合物的合成和表征
DOI：
10.1039/dt9930002645
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发表时间：
1993
期刊：
影响因子：
--
通讯作者：
S. Yano
中科院分区：
文献类型：
--
作者：
T. Tanase;R. Nouchi;Y. Oka;Masako Kato;N. Nakamura;T. Yamamura;Yasuhiro Yamamoto;S. Yano
[Ni(tn)3]2+离子（tn = 1,3-二氨基丙烷）与具有葡萄糖还原末端的二糖，即麦芽糖、乳糖、纤维素二糖和二糖，在一定催化量的氯化铵存在下反应得到蓝色顺磁性双（n -d -醛基丙烷-1,3-二胺）镍（II）配合物。通过元素分析、磁化率、电子吸收和圆二色光谱、x射线吸收和晶体学分析对配合物进行了表征。配合物[N-（4-O-α- d -葡萄糖基葡萄糖基）丙烷-1,3-二胺]溴化镍二水合物在六方空间群P6422中结晶，a= 22.125(8), c= 21.464(9) a， Z= 6。采用Patterson方法对结构进行求解，并利用全矩阵最小二乘技术将其细化为R= 0.080和R ' = 0.094。配合物阳离子具有C2对称，中心镍原子由麦芽糖和n形成的两个三齿糖胺配体八面体配位。每个配体通过麦芽糖C2羟基的氧原子和二胺的两个氮原子以子午模式结合。葡萄糖单元在八面体镍（II）配合物中的配位行为已经确定。在晶体填料中，配合阳离子以一种新的二聚体形式存在于分子间氢键的支持下，这可能为生物系统中糖-糖相互作用提供一些基本信息。
The reaction of [Ni(tn)3]2+ ions (tn = 1,3-diaminopropane) with disaccharides having a glucose reducing terminal, i.e. maltose, lactose, cellobiose, and melibiose, in the presence of a catalytic amount of ammonium chloride gave blue, paramagnetic bis(N-D-aldosylpropane-1,3-diamine)nickel(II) complexes. The complexes were characterized by elemental analysis, magnetic susceptibilities, electronic absorption and circular dichroism spectroscopies, X-ray absorption and crystallographic analyses. The complex bis[N-(4-O-α-D-glucopyranosylglucosyl)propane-1,3-diamine]nickel(II) bromide dihydrate crystallizes in the hexagonal space group P6422, with a= 22.125(8), c= 21.464(9)A, and Z= 6. The structure was solved by Patterson methods and refined by full-matrix least-squares techniques to R= 0.080 and R′= 0.094. The complex cation has C2 symmetry and the central nickel atom is octahedrally co-ordinated by two tridentate glycosylamine ligands formed from maltose and tn. Each ligand is bonded through the oxygen atom of the hydroxyl group at C2 of maltose and through the two nitrogen atoms of the diamine in a meridional mode. The co-ordination behaviour of the glucose unit in the octahedral nickel(II) complexes has been established. In the crystal packing, the complex cation exists in a novel dimeric form supported by intermolecular hydrogen bonds, which might provide some fundamental information concerning sugar–sugar interactions in biological systems.