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Fate of model complexes with monocopper center towards the functional properties of type 2 and type 3 copper oxidases

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Abstract

Green colored mononuclear copper(II) complexes viz. [Cu(L)(bpy)](ClO4) (1) or [Cu(L)(phen)](ClO4) (2) (where H(L) is 2-((2-dimethylamino)ethyliminomethyl)naphthol) show distorted square pyramidal (4 + 1) geometry with CuN4O chromophore. The existence of self-assembled molecular associations indicates the formation of the dimer. Dimeric nature in solution is retained due to the binding of the substrate, encourages steric match between substrate and Cu(II) active site, which favors electron transfer. Interestingly, both the complexes exhibit high-positive redox potential. Therefore, the presence of self-assembled molecular association along with the positive redox potential enhances the catalytic oxidation of ascorbic acid to dehydroascorbic acid or benzylamine to benaldehyde or catechol to o-quinone thereby model the functional properties of type 2 and type 3 copper oxidases. Notably, catalytic activity is effective when compared with other reported mononuclear copper(II) complexes and even superior to many binuclear copper(II) complexes.

Graphic abstract

Existence of self-assembled molecular association in solution along with high-positive redox potential favors electron transfer process in mononuclear copper(II) complexes and models the functional properties of type 2 and type 3 copper oxidases.

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Acknowledgements

We thank the Science and Engineering Research Board, New Delhi (Grant No. EMR/2016/007756) for the financial support. Thanks are due to STIC, Cochin University of Science and Technology for X-ray crystal structure data. We thank SAIF, Indian Institute of Technology Madras for structure solution and refinement and for recording EPR spectra.

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  1. Coordination and Bioinorganic Chemistry Research Laboratory, Department of Chemistry, National College (Autonomous), Tiruchirappalli, Tamil Nadu, 620 001, India

    Mariappan Murali, Velusamy Sathya & Balasubramaniam Selvakumaran

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Murali, M., Sathya, V. & Selvakumaran, B. Fate of model complexes with monocopper center towards the functional properties of type 2 and type 3 copper oxidases. J Biol Inorg Chem 26, 67–79 (2021). https://doi.org/10.1007/s00775-020-01837-5

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