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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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Cobalt in a bis-β-diketiminate environment.

Michael P Marshak1, Matthew B Chambers, Daniel G Nocera

  • 1Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.

Inorganic Chemistry
|September 28, 2012
PubMed
Summary

This study details the synthesis of a novel cobalt(II) complex with a planar, low-spin bis-β-diketiminate structure. Oxidation studies reveal the ligand

Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Coordination Chemistry

Background:

  • Bis-β-diketiminate ligands are versatile in coordination chemistry.
  • Cobalt complexes exhibit diverse electronic and magnetic properties.

Purpose of the Study:

  • To synthesize and characterize a novel bis-β-diketiminate cobalt(II) complex.
  • To investigate the electronic structure and redox behavior of the cobalt complex.
  • To explore the role of the ligand in redox processes.

Main Methods:

  • Reaction of Co(2)(mesityl)(4) with acetonitrile.
  • Electron Paramagnetic Resonance (EPR) spectroscopy.
  • Magnetic susceptibility studies.
  • Density Functional Theory (DFT) calculations.

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  • X-ray crystallography.

    • Main Results:

    • Formation of a planar, low-spin, bis-β-diketiminate cobalt(II) complex, (1-mesitylbutane-1,3-diimine)(2)Co (1).
    • Characterization of a (2)B(2)(d(yz))(1) ground state electronic configuration in a tetragonal ligand field.
    • Successful oxidation to a cobalt(III) complex, (1-mesitylbutane-1,3-diimine)(2)Co(THF)(2)PF(6) (2).
    • X-ray crystal structures indicate minimal changes in metal-ligand bond lengths upon oxidation, suggesting ligand participation.

    Conclusions:

    • The synthesized cobalt(II) complex exhibits a unique electronic configuration.
    • The β-diketiminate ligand demonstrates redox non-innocence, participating in the oxidation event.
    • This contrasts with typical redox non-innocent ligand behaviors, highlighting unique properties.