Jyotiprokash Biswas, Sebastian Sanden, Prabhakar Bhardwaj, Daniel Siegmund, Pankaj Kumar and Ulf-Peter Apfel
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引用次数: 0
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.
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.