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Mercury(IV) fluoride



  Mercury(IV) fluoride, HgF4, is the first mercury compound to be discovered with the metal in the oxidation state IV. Mercury, like the other group 12 elements (cadmium and zinc), has an s2d10 electron configuration and generally only forms bonds involving its s orbital. This means that the highest oxidation state mercury normally attains is II, and for this reason it is generally considered a post-transition metal instead of a transition metal.

Additional recommended knowledge

Speculation about higher oxidation states for mercury had been around since the 1970s, and theoretical calculations in the 1990s predicted that it should be stable in the gas phase, with a square-planar geometry consistent with a formal d8 configuration. However, experimental proof remained elusive until 2007, when HgF4 was first prepared using solid neon and argon for matrix isolation at a temperature of 4 K. The compound was detected using infrared spectroscopy. Analysis of density functional theory and coupled cluster calculations showed that the d orbitals are involved in bonding, leading to the suggestion that mercury should be considered a transition metal after all. The predicted bond length in HgF4 is 188.5 pm, compared with 191.4 pm for HgF2.

Theoretical studies suggest that mercury is unique among the natural elements of group 12 in forming a tetrafluoride, and attribute this observation to relativistic effects. According to calculations, the tetrafluorides of the "less relativistic" elements cadmium and zinc are unstable and eliminate a fluorine molecule, F2, to form the metal difluoride. On the other hand, the tetrafluoride of the "more relativistic" synthetic element 112, ununbium, is predicted to be more stable.

References

  • Xuefang Wang; Lester Andrews; Sebastian Riedel; and Martin Kaupp (2007). "Mercury Is a Transition Metal: The First Experimental Evidence for HgF4.". Angew. Chem. Int. Ed. 46 (44): 8371–8375. doi:10.1002/anie.200703710.
  • Elusive Hg(IV) species has been synthesized under cryogenic conditions (2007-10-12).
  • High Oxidation States: Mercury tetrafluoride synthesized.
 
This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Mercury(IV)_fluoride". A list of authors is available in Wikipedia.
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