A terpyridine-based copper complex for electrochemical reduction of nitrite to nitric oxide†

IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Jyotiprokash Biswas, Sebastian Sanden, Prabhakar Bhardwaj, Daniel Siegmund, Pankaj Kumar and Ulf-Peter Apfel
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Abstract

In biological systems, nitrite reductase enzymes (NIRs) are responsible for reduction of nitrite (NO2) to nitric oxide (NO). These NIRs have mostly Cu- or Fe-containing active sites, surrounded by amine-containing ligands. Therefore, mononuclear Cu complexes with N-donor ligands are highly relevant in the development of NIR model systems and in the mechanistic investigation of the nitrite reduction reaction. Herein, we report on a terpyridine-based CuII complex with square planar geometry for H+-assisted electrochemical reduction of NO2. Through electrochemical measurements, spectroscopic characterization and isotope-labelling experiments we propose a mechanistic reaction pathway involving an unstable HNO2 state. The CuI intermediate, formed electrochemically, was isolated and its molecular structure was deduced, showing linkage isomerism of the nitrite ligand. Moreover, qualitative and quantitative product analysis by GC-MS shows N2O formed as a side product along with the main product NO. Furthermore, by obtaining single crystals and conducting structural analysis we were able to determine the structural arrangement and redox state of the complex after electrochemical treatment.

Abstract Image

以三联吡啶为基础的铜配合物电化学还原亚硝酸盐为一氧化氮
在生物系统中,亚硝酸盐还原酶(NIRs)负责将亚硝酸盐(NO2-)还原为一氧化氮(NO)。这些近红外光谱大多含有含铜或铁的活性位点,被含胺的配体包围。因此,单核Cu配合物与n给体配体在近红外模型体系的开发和亚硝酸盐还原反应机理研究中具有重要意义。本文报道了一种基于三吡啶的方形几何形状的CuII配合物,用于H+辅助电化学还原NO2-。通过电化学测量、光谱表征和同位素标记实验,我们提出了一个涉及不稳定HNO2状态的机理反应途径。对电化学生成的CuI中间体进行了分离,并对其分子结构进行了推断,表明其为亚硝酸盐配体的连锁异构。通过GC-MS对产物进行定性和定量分析,发现N2O是伴随主产物NO形成的副产物。此外,通过获得单晶和结构分析,我们成功地确定了电化学处理后复合物的结构排列和氧化还原状态。
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来源期刊
Dalton Transactions
Dalton Transactions 化学-无机化学与核化学
CiteScore
6.60
自引率
7.50%
发文量
1832
审稿时长
1.5 months
期刊介绍: Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
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