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Related Experiment Videos

Dioxygen activation at monovalent nickel.

Matthew T Kieber-Emmons1, Charles G Riordan

  • 1Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.

Accounts of Chemical Research
|May 24, 2007
PubMed
Summary
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Nickel(I) complexes activate dioxygen, forming novel superoxo and peroxo structures. These findings advance understanding of nickel

Area of Science:

  • Inorganic Chemistry
  • Bioinorganic Chemistry
  • Coordination Chemistry

Background:

  • Growing interest in the monovalent nickel oxidation state, particularly its catalytic roles in metalloprotein transformations.
  • Nickel(I) is a promising candidate for reductive activation of dioxygen.
  • Stabilizing ligands are crucial to prevent disproportionation of the less common nickel(I) state.

Purpose of the Study:

  • To explore molecular systems enabling the stabilization and reactivity of nickel(I) with dioxygen.
  • To synthesize and characterize novel nickel-dioxygen complexes.
  • To investigate the structural and electronic properties of these new complexes.

Main Methods:

  • Synthesis of two distinct molecular systems involving nickel(I) and dioxygen.

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  • Characterization using advanced spectroscopic techniques, including resonance Raman and X-ray absorption spectroscopy.
  • Computational analysis using density functional theory (DFT) to complement experimental data.

    • Main Results:

    • Successful synthesis of novel nickel-dioxygen complexes.
    • Identification of monomeric side-on and end-on superoxo structures.
    • Discovery of trans-micro-1,2-peroxo-dinickel complexes.
    • Detailed elucidation of geometric and electronic structures.

    Conclusions:

    • The study provides access to new nickel-dioxygen structural motifs.
    • Demonstrates the feasibility of stabilizing nickel(I) for dioxygen activation.
    • Highlights the importance of ligand design in controlling nickel reactivity and structure.