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Fixation and sequestration of carbon dioxide by copper(II) complexes

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Abstract

Abstract

The fixation of carbon dioxide (\(\hbox {CO}_{2})\) is an important global challenge. A significant increase of the atmospheric \(\hbox {CO}_{2}\) due to the industrial emissions and a steady increase in combustion of fossil fuels is a widespread environmental concern. This article is a short literature review on the recent developments in the field of \(\hbox {CO}_{2}\) activation and fixation by bioinspired copper(II) catalysts. In our laboratory, copper(II) complexes of bidentate ligands have been reported as catalysts for the fixation of \(\hbox {CO}_{2}\). The molecular structure of one of the complexes has shown unusual trigonal bipyramid geometry (\(\tau \), 0.936) by the coordination of two ligand units and a water molecule. All the complexes exhibited a well-defined Cu(II)/Cu(I) redox potentials around 0.352 to 0.401 V in acetonitrile. The rhombic EPR spectra of the complexes indicate the existence of a geometrical equilibrium between trigonal bipyramidal and square pyramidal at 70 K. The d-d transitions around 750–800 and 930–955 nm further supports five coordination geometry in solution. These copper(II) complexes have successfully fixed atmospheric \(\hbox {CO}_{2}\) as \(\hbox {CO}_{3}^{2-}\) by using \(\hbox {Et}_{3}\hbox {N}\) as sacrificial reducing agent and afforded [\(\hbox {Cu(L)CO}_{3}\)(\(\hbox {H}_{2}\hbox {O}\))]. The \(\hbox {CO}_{3}^{2-}\) bound complex has shown a distorted square pyramidal geometry (\(\tau \), 0.369) around copper(II) center via the coordination of only one ligand unit, a carbonate, and water molecules. The catalysts are active enough to fix \(\hbox {CO}_{2}\) for eight repeating cycles without any change in the efficiency. The fixation of \(\hbox {CO}_{2}\) possibly proceeds via the formation of Cu(I)-species. This is supported by X-ray structure, which reveals distorted tetrahedral geometry by the coordination of two units of ligand.

GRAPHICAL ABSTRACT

SYNOPSIS The fixation of carbon dioxide (\(\hbox {CO}_{2})\) is an important global challenge. This review summarizes the recent developments in \(\hbox {CO}_{2}\) fixation by bioinspired Cu(II) catalysts.

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Acknowledgements

We acknowledge Science and Engineering Research Board (SERB), New Delhi and Board of Research in Nuclear Science (BRNS), Mumbai for funding.

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Authors and Affiliations

  1. Bioinorganic Chemistry Laboratory/Physical Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai, Tamilnadu, 625 021, India

    Sethuraman Muthuramalingam & Ramasamy Mayilmurugan

  2. Department of Chemistry, North Eastern Hill University, Shillong, Meghalaya, 793 022, India

    Marappan Velusamy

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  1. Sethuraman Muthuramalingam
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Correspondence to Ramasamy Mayilmurugan.

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Special Issue on Modern Trends in Inorganic Chemistry

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Muthuramalingam, S., Velusamy, M. & Mayilmurugan, R. Fixation and sequestration of carbon dioxide by copper(II) complexes. J Chem Sci 130, 78 (2018). https://doi.org/10.1007/s12039-018-1489-1

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