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首页> 外文期刊>Chemistry: A European journal >Templated Synthesis of Copper(II) Azacyclam Complexes Using Urea as a Locking Fragment and Their Metal-Enhanced Binding Tendencies towards Anions
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Templated Synthesis of Copper(II) Azacyclam Complexes Using Urea as a Locking Fragment and Their Metal-Enhanced Binding Tendencies towards Anions

机译：使用尿素作为锁定片段及其对阴离子的金属增强结合趋势的模板化合成铜（II）氮杂阿西酰胺配合物

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摘要

Copper(II) azacyclam complexes 32+ and 42+ were obtained through a metal-templated procedure involving the pertinent open-chain tetramine, formaldehyde and a phenylurea derivative as a locking fragment. Both metal complexes can establish interactions with anions through the metal centre and the amide NH group. Equilibrium studies in DMSO by a spectrophotometric titration technique were carried out to assess the affinity of 32+ and 42+ towards anions. While the NH group of an amide model compound and the metal centre of the plain CuII(azacyclam)2+ complex do not interact at all with anions, 32+ and 42+ establish strong interactions with oxo anions, profiting from a pronounced cooperative effect. In particular, 1) they form stable 1:1 and 1:2 complexes with H2PO4 ions in a stepwise mode with both hydrogen-bonding and metal–ligand interactions, and 2) in the presence of CH3COO, they undergo deprotonation of the amido NH group and thus profit from axial coordination of the partially negatively charged carbonyl oxygen atom in a scorpionate binding mode.
机译：通过金属模板化程序获得铜（II）氮杂环十二烷络合物32+和42+，该方法涉及相关的开链四胺，甲醛和苯基脲衍生物作为锁定片段。两种金属络合物均可通过金属中心和酰胺NH基团与阴离子建立相互作用。通过分光光度滴定技术在DMSO中进行了平衡研究，以评估32+和42+对阴离子的亲和力。虽然酰胺模型化合物的NH基团和纯CuII（氮杂环磷酰胺）2+配合物的金属中心根本不与阴离子相互作用，但32+和42+与氧代阴离子建立了牢固的相互作用，这得益于明显的协同作用。特别是：1）它们与氢分子和金属-配体相互作用的逐步模式与H2PO4离子形成稳定的1：1和1：2络合物，以及2）在CH3COO存在下，它们会使酰胺基NH脱质子化基团，因此得益于在蝎形结合模式下部分带负电荷的羰基氧原子的轴向配位。

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