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High-valent osmium iminoxolene complexes.

Jacqueline Gianino1, Alexander N Erickson1, Sean J Markovitz1

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New osmium(VI) complexes with amidophenoxide ligands were synthesized. These square pyramidal complexes exhibit varying ligand-to-metal π-donation, influencing their electronic structure and bonding properties.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Osmium Chemistry

Background:

  • Amidophenol ligands are versatile in coordination chemistry.
  • Osmium complexes exhibit diverse oxidation states and coordination geometries.

Purpose of the Study:

  • To synthesize and characterize novel osmium(VI) amidophenoxide complexes.
  • To investigate the electronic properties and bonding in these complexes.

Main Methods:

  • Reaction of 2-(arylamino)-4,6-di-tert-butylphenols with osmium precursors.
  • Synthesis of mono- and bis(amidophenoxide) osmium complexes.
  • Characterization using spectroscopic techniques.

Main Results:

  • Square pyramidal bis(amidophenoxide)oxoosmium(VI) complexes were formed.
  • A mono-amidophenoxide complex was identified as an intermediate.
  • Complexes with diolate and cis-dichloride ligands were also synthesized.
  • Ligand-to-metal π-donation increases from oxo to diolate to dichloride ligands.

Conclusions:

  • The electronic structure of osmium-amidophenoxide complexes is tunable via co-ligands.
  • Osmium(VI)-amidophenoxide formulation accurately describes the complexes.
  • Ligand π-orbital symmetry influences osmium-oxo bonding anisotropy.