Gold with +4 and +6 Oxidation States in AuF4 and AuF6
Citations Over TimeTop 10% of 2018 papers
Abstract
An important goal in chemistry is to prepare compounds with unusual oxidation states showing exciting properties. For gold (Au), the relativistic expansion of its 5d orbitals makes it form high oxidation state compounds. Thus far, the highest oxidation state of Au known is +5. Here, we propose high pressure as a controllable method for preparing +4 and +6 oxidation states in Au via its reaction with fluorine. First-principles swarm-intelligence structure search identifies two hitherto unknown stoichiometric compounds, AuF4 and AuF6, exhibiting typical molecular crystal character. The high-pressure phase diagram of Au fluorides is rather different from Cu or Ag fluorides, which is indicated by stable chemical compositions and the pressures needed for the synthesis of these compounds. This difference can be associated with the stronger relativistic effects in Au relative to Cu or Ag. Our work represents a significant step forward in a more complete understanding of the oxidation states of Au.
Related Papers
- → X-ray photoelectron spectroscopy as detection tool for coordinated or uncoordinated fluorine atoms demonstrated on fluoride systems NaF, K2TaF7, K3TaF8, K2ZrF6, Na7Zr6F31 and K3ZrF7(2012)30 cited
- → Study of the synthesis process of non-stoichiometric TiC in Cu-Ti melts(2018)8 cited
- → A positive “through-space” fluorine-fluorine coupling constant in perfluorotoluene(1975)9 cited
- → On the calculation of fluorine-fluorine coupling constants in fluorinated propenes(1974)4 cited
- Laser induced oxidation and optical properties of stoichiometric and non-stoichiometric Bi2Te3 nanoplates(2015)