Tungsten hexachloride

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Tungsten hexachloride
Tungsten hexachloride
IUPAC name Tungsten(VI) chloride
Other names Tungsten hexachloride
Identifiers
CAS number [13283-01-7]
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 other solvents chlorocarbons
Structure
Crystal structure α:rhombohedral, β: hexagonal
Coordination
geometry
octahedral
Dipole moment 0 D
Hazards
Main hazards oxidizer
hydrolysis releases HCl
R-phrases 34
S-phrases 26-36/37/39-45
Related compounds
Related compounds Molybdenum(V) chloride
chromyl chloride
tungsten hexafluoride
Except where noted otherwise, data are given for
materials in their standard state
(at 25 °C, 100 kPa)

Infobox disclaimer and references

Tungsten hexachloride is the chemical compound 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. MoCl6 cannot be prepared. 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 the 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).

[edit] Safety considerations

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

[edit] 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.; Coll. Vol. 7: 121.