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Tungsten hexachloride
Tungsten hexachloride
IUPAC name
Identifiers
CAS number 13283-01-7 Yes check.svgY
RTECS number YO7710000
Properties
Molecular formula WCl6
Molar mass 396.61 g/mol
Appearance dark blue crystals, moisture sensitive
Density 3.52 g/cm3
Melting point

275 °C

Boiling point

346.7 °C

Solubility in water hydrolyzes
Solubility in chlorocarbons soluble
Structure
Crystal structure α:rhombohedral, β: hexagonal
Coordination
geometry
octahedral
Dipole moment 0 D
Hazards
EU Index Not listed
Main hazards oxidizer; hydrolysis releases HCl
Related compounds
Other anions Tungsten hexafluoride
Tungsten hexabromide
Other cations Molybdenum(V) chloride
Chromyl chloride
 Yes check.svgY (what is this?)  (verify)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Tungsten hexachloride is the chemical compound of tungsten and chlorine with the formula WCl6. This dark violet blue species exists as a volatile solid under standard conditions. It is an important starting reagent in the preparation of tungsten compounds.[1] WCl6 is a rare example of a charge-neutral hexachloride, another example being ReCl6. Better known than WCl6 is the still more volatile WF6.

As a d0 ion, W(VI) forms diamagnetic derivatives. The hexachloride is octahedral with equivalent W-Cl distances of 2.24 - 2.26 Å.[2] In WCl6, the chloride ligands are donors in both sigma- and pi sense. Methylation with trimethylaluminium affords hexamethyl tungsten. Treatment with butyl lithium affords a reagent that is useful for deoxygenation of epoxides.[3]

The chloride ligands in WCl6 can be replaced by many anionic ligands including Br, NCS, and RO (R = alkyl, aryl).

Safety considerations

WCl6 is an aggressively corrosive oxidant, and hydrolyzes to release hydrogen chloride.

References

  1. ^ J. W. Herndon "Tungsten(VI) Chloride” in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289.
  2. ^ J. C. Taylor and P. W. Wilson "The structure of [beta]-tungsten hexachloride by powder neutron and X-ray diffraction" Acta Crystallographic (1974). B30, 1216-1220.doi:10.1107/S0567740874004572.
  3. ^ M. A. Umbreit, K. B. Sharpless (1990), "Deoxygenation of Epoxides with Lower Valent Tungsten Halides: trans-Cyclododecene", Org. Synth., http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV7P0121  ; Coll. Vol. 7: 121  
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