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一种用于瞬间裂解碳-碳键并同时将酮还原为醇的锌(II)配位聚合物。

A Zn(II)-Coordination Polymer for the Instantaneous Cleavage of C-C Bond and Simultaneous Reduction of Ketone to Alcohol.

作者信息

Ghosh Debasish, Dhibar Subhendu, Gupta Vivek K, Das Gourab Kanti, Dey Biswajit

机构信息

Department of Chemistry, Visva-Bharati University, Santiniketan-731235, India.

Post-Graduate Department of Physics, University of Jammu, Jammu Tawi-180006, India.

出版信息

Inorg Chem. 2020 Apr 20;59(8):5350-5356. doi: 10.1021/acs.inorgchem.9b03441. Epub 2020 Apr 1.

Abstract

Two coordination polymers of Zn(II) and Cu(II) with -butylmalonic acid have been achieved in this work. The crystallographic structural descriptions along with the sedimentary rock-type microstructural morphology of these two coordination polymers (CPs) have been explored. The reactivity of β-hydroxy ketones with these two CPs has also been investigated. The Zn(II)-CP shows a specific reactivity with β-hydroxy ketone at room temperature and in open air conditions. Through a microcolumn-based filtration technique, the Zn(II)-CP shows the capability to break the C-C σ bonds of β-hydroxy ketone and simultaneously reduce the associated ketone to alcohol. Such conversion has been progressed without the use of any additional external reducing agent and any chemical workup or column chromatographic purification protocol. Other similar type CPs of Cu(II) and Mn(II) with -butylmalonic acid completely failed to show similar reactivity with β-hydroxy ketone. On the basis of much experimental evidence, the most possible mechanistic pathway of the reactivity between β-hydroxy ketone and Zn(II)-CP has also been proposed through this work.

摘要

在本研究中,已成功制备出两种锌(II)和铜(II)与正丁基丙二酸形成的配位聚合物。对这两种配位聚合物的晶体结构描述以及沉积岩型微观结构形态进行了探索。还研究了β-羟基酮与这两种配位聚合物的反应活性。锌(II)配位聚合物在室温及露天条件下对β-羟基酮表现出特定的反应活性。通过基于微柱的过滤技术,锌(II)配位聚合物显示出能够断裂β-羟基酮的C-C σ键,并同时将相关的酮还原为醇的能力。这种转化在不使用任何额外外部还原剂以及任何化学后处理或柱色谱纯化方案的情况下得以进行。其他类似类型的铜(II)和锰(II)与正丁基丙二酸的配位聚合物完全未能显示出与β-羟基酮类似的反应活性。基于大量实验证据,通过本研究还提出了β-羟基酮与锌(II)配位聚合物反应活性最可能的机理途径。

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