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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Controlled in situ reaction for the assembly of Cu( II) mixed-ligand coordination polymers: synthesis, structure, mechanistic insights, magnetism and catalysis
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Controlled in situ reaction for the assembly of Cu( II) mixed-ligand coordination polymers: synthesis, structure, mechanistic insights, magnetism and catalysis

机译：铜（II）混合配体配位聚合物组装的受控原位反应：合成，结构，机理见解，磁性和催化作用

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摘要

It has been a challenge to decipher the in situ ligand reaction mechanism in assembly processes, involving metals and ligands. The present study shows two crystalline mixed-ligand Cu(II) coordination polymers isolated by controlled in situ ligand reactions under the same hydrothermal conditions. Two closely related examples provide a precious chance to access the in-depth mechanistic issues surrounding in situ reactions. The solid structure of 1 demonstrated that maleic acid was completely transformed to malic acid, whereas when fumaric acid was used in the same reaction conditions, an incomplete transformation from fumaric acid to malic acid was observed in the solid structure of 2. Compound 1 exhibits a 3D 6-connected sni network based on a binuclear copper(II) secondary building unit, whereas the 3D network of 2 is classified to a (6,8)-connected topology network. The difference in steric hindrance between maleic acid and fumaric acid dictates the degree of the in situ nucleophilic addition reaction. The comparison of synthesis and final solid structures indicates that the one-step nucleophilic addition mechanism for in situ generated malic acid under the current reaction conditions of 1 is plausible. The magnetic sensitivity measurements of 1 demonstrated that overall antiferromagnetic coupling exists between Cu1 and Cu2 ions and between Cu3 and Cu4 ions. Furthermore, the obtained 1 can be an active catalyst for the solvent-free silylcyanation of aromatic aldehydes under mild conditions.
机译：在组装过程中破译涉及金属和配体的原位配体反应机理一直是一个挑战。本研究显示了在相同的水热条件下通过受控的原位配体反应分离出的两种晶体混合配体Cu（II）配位聚合物。两个密切相关的例子为了解围绕原位反应的深入机理问题提供了宝贵的机会。 1的固体结构表明马来酸已完全转化为苹果酸，而在相同的反应条件下使用富马酸时，在2的固体结构中观察到了从富马酸到苹果酸的不完全转化。基于双核铜（II）二级建筑单元的3D 6连接sni网络，而2的3D网络则分类为（6,8）连接的拓扑网络。马来酸和富马酸之间的空间位阻差异决定了原位亲核加成反应的程度。合成和最终固体结构的比较表明，在当前反应条件为1的条件下，原位生成苹果酸的一步亲核加成机理是合理的。 1的磁灵敏度测量结果表明，Cu1和Cu2离子之间以及Cu3和Cu4离子之间存在总体反铁磁耦合。此外，所获得的1可以是在温和条件下用于芳族醛的无溶剂甲硅烷基氰化的活性催化剂。

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