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Terminal gold-oxo complexes.

Rui Cao1, Travis M Anderson, Paula M B Piccoli

  • 1Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.

Journal of the American Chemical Society
|August 23, 2007
PubMed
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Two novel gold-oxo molecular complexes were synthesized, challenging current bonding theories. These complexes feature short gold-oxo bonds and stabilized gold(III) centers, confirmed by various spectroscopic and diffraction methods.

Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Coordination Chemistry

Background:

  • Current bonding paradigms in inorganic chemistry.
  • Understanding the behavior of metal oxide surfaces and their interactions with metal ions.
  • The synthesis and characterization of novel molecular complexes.

Purpose of the Study:

  • To synthesize and characterize new terminal gold-oxo molecular complexes.
  • To investigate the bonding characteristics of gold-oxo interactions.
  • To model redox-active metal oxide surfaces using molecular complexes.

Main Methods:

  • Synthesis of gold-oxo complexes using gold(III) chloride and polytungstate ligands.
  • X-ray diffraction and neutron diffraction for structural determination.

Related Experiment Videos

  • Redox titrations, electrochemistry, optical spectroscopy, X-ray absorption spectroscopy (XAS), NMR spectroscopy, FT-IR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) for characterization.

    • Main Results:

    • Two terminal Au-oxo molecular complexes, K15H2[Au(O)(OH2)P2W18O68].25H2O (1) and K7H2[Au(O)(OH2)P2W20O70(OH2)2].27H2O (2), were successfully synthesized.
    • X-ray and neutron diffraction confirmed very short Au-oxo bond distances (approx. 1.76 Å) and the presence of oxo and aqua ligands on gold.
    • Multiple spectroscopic and electrochemical techniques provided evidence for stabilized d8 Au(III) centers and diamagnetic properties in both solution and solid states.

    Conclusions:

    • The synthesized gold-oxo complexes challenge existing bonding paradigms.
    • The complexes serve as valuable models for redox-active metal oxide surfaces.
    • The study provides comprehensive characterization of novel gold-oxo compounds, highlighting their unique electronic and structural properties.