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Dioxygen bound cobalt corroles.

Kaustuv Mittra1, Biswajit Mondal1, Atif Mahammed2

  • 1Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata, India 700032. icad@iacs.res.in.

Chemical Communications (Cambridge, England)
|December 23, 2016
PubMed
Summary
This summary is machine-generated.

Two cobalt-dioxygen adducts, stabilized by electron-rich and electron-poor corroles, were characterized. These complexes exhibit (corrole) cobalt(iii)-superoxo structures, crucial for tuning electrocatalysts for efficient oxygen reduction.

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Area of Science:

  • Inorganic Chemistry
  • Electrochemistry
  • Spectroscopy

Background:

  • Cobalt corrole complexes are investigated for their potential in oxygen reduction reactions.
  • Understanding the electronic structure of cobalt-dioxygen adducts is key to designing efficient catalysts.

Purpose of the Study:

  • To synthesize and characterize cobalt-dioxygen adducts with varying electronic properties of the corrole ligand.
  • To elucidate the electronic structure and bonding in these adducts using spectroscopic and computational methods.
  • To assess their potential as electrocatalysts for molecular oxygen reduction.

Main Methods:

  • Isolation and characterization of cobalt-dioxygen adducts in solution.
  • Resonance Raman (rR) and Electron Paramagnetic Resonance (EPR) spectroscopy.
  • Density Functional Theory (DFT) analyses.

Main Results:

  • Two cobalt-dioxygen adducts, [CoH8]-O2 and [CoCl8]-O2, were successfully isolated.
  • Spectroscopic and DFT data confirm (corrole) cobalt(iii)-superoxo structures.
  • Subtle differences in Co-O and O-O bond strengths were observed, with the electron-rich ligand ([CoH8]-O2) showing a slightly stronger Co-O bond and weaker O-O bond.

Conclusions:

  • The electronic properties of the corrole ligand subtly influence the cobalt-dioxygen interaction.
  • These cobalt complexes are promising candidates for electrocatalysts in oxygen reduction, tunable for high activity and low overpotential.