首页> 外文期刊>Inorganica Chimica Acta >Solution properties of the nickel(II,III) and copper(II,III) complexes of trans-dioxocyclam (trans-dioxocyclam=5,12-dioxo-1,4, 8,11-tetraazacyclotetradecane) and the X-ray crystal structure of the N-rac-isomer of the nickel(II) complex
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Solution properties of the nickel(II,III) and copper(II,III) complexes of trans-dioxocyclam (trans-dioxocyclam=5,12-dioxo-1,4, 8,11-tetraazacyclotetradecane) and the X-ray crystal structure of the N-rac-isomer of the nickel(II) complex

机译:反式二氧杂环丁烷(反式二氧杂环丁烷= 5,12-二氧杂-1,4,8,11-四氮杂环十四烷)的镍(II,III)和铜(II,III)配合物的溶液性质和X射线晶体结构镍(II)配合物的N-rac-异构体的合成

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The crystal and molecular structures of the N-rac-isomer of the nickel(II) complex of 14-membered amide-containing macrocycle [NiL1].4H(2)O (H2L1=5,12-dioxo-1,4,8,11-tetraazacyclotetradecane) have been determined. Two deprotonated amide and two amine donors co-ordinate to the nickel(II) in nearly square planar manner with Ni-N-amine bonds longer than Ni-N-amide ones (1.930 vs. 1.898 Angstrom). Water molecules do not co-ordinate and form hydrogen bond bridges between macrocyclic units in the crystal lattice. The analysis of H-1 NMR data confirmed that the solid-state conformation of the macrocycle in N-rac[NiL1] is retained in aqueous solution though equilibrated with some amount of N-meso isomer. The comparison of the spectroscopic characteristics of the M(II) and M(III) complexes and the redox potentials of M(III/II) couples (M=Ni and Cu) for ML1 with those for ML2-(H2L2-=5,7dioxo-1,4,8,11-tetraazacyclotetradecane) revealed a rather small influence of the trans- vs. cis-arrangement of amide donors in coordination spheres of the metal ions. (C) 2003 Elsevier B.V. All rights reserved. [References: 50]
机译:14元含酰胺大环[NiL1] .4H(2)O(H2L1 = 5,12-dioxo-1,4,8)的镍(II)配合物的N-rac-异构体的晶体和分子结构(11-四氮杂环十四烷)已被确定。两个去质子化的酰胺和两个胺供体以近似正方形平面的方式与镍(II)配位,且Ni-N-胺键的长度比Ni-N-酰胺键的长(1.930对1.898埃)。水分子不配位并在晶格中的大环单元之间形成氢键桥。 H-1 NMR数据分析证实,N-rac [NiL1]中大环的固态构型虽然与一定量的N-内消旋异构体平衡,但仍保留在水溶液中。 ML1与ML2-(H2L2- = 5)的M(II)和M(III)配合物的光谱特性和M(III / II)对(M = Ni和Cu)的氧化还原电位的比较, 7dioxo-1,4,8,11-四氮杂环十四烷)显示出酰胺供体在金属离子配位领域中反式-顺式排列的影响很小。 (C)2003 Elsevier B.V.保留所有权利。 [参考:50]

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