Tungsten(VI) oxytetrachloride

Tungsten(VI) oxytetrachloride is the inorganic compound with the formula WOCl4. This diamagnetic solid is used to prepare other complexes of tungsten. The yellow-green compound is soluble in nonpolar solvents but it reacts with alcohols and water and forms adducts with Lewis bases.

Tungsten(VI) oxytetrachloride
Names
Other names
Tungsten(IV) chloride oxide
Identifiers
3D model (JSmol)
ECHA InfoCard 100.033.497
Properties
WOCl4
Molar mass 341.651 g/mol
Appearance red crystals
Density 11.92 g/cm3
Melting point 211 °C (412 °F; 484 K)
Boiling point 227.55 °C (441.59 °F; 500.70 K)
reacts
Solubility soluble in benzene and CS2
Hazards
not listed
Related compounds
Other anions
Tungsten(VI) oxytetrafluoride
Tungsten(VI) oxytetrabromide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references


Structure

Structure of solid WOCl4, illustrating its polymeric structure with short WO and weak W---O bonds in the chains. Color code: O = red.

The solid consists of weakly associated square pyramidal monomers.[1] The compound is classified as an oxyhalide.

Synthesis and reactions

WOCl4 is prepared from tungsten trioxide:[2]

WO3 + 2 SOCl2 → WOCl4 + 2 SO2
WCl6 + (Me3Si)2O → WOCl4 + 2 Me3SiCl

WOCl4 is Lewis acidic. It is a precursor to catalysts used for polymerization of alkynes.[3]

References

  1. Hess, H.; Hartung, H. (1966). "Die Kristallstruktur von Wolframoxidchlorid WOCl4 und Wolframoxidbromid WOBr4". Z. Anorg. Allg. Chem. 34 (3–4): 157–166. doi:10.1002/zaac.19663440306.
  2. Nielson, A. J. (1985). "Tungsten and Molybdenum Tetrachloride Oxides". Inorganic Syntheses. Inorg. Synth. Inorganic Syntheses. 23. pp. 195–198. doi:10.1002/9780470132548.ch41. ISBN 9780470132548.
  3. Hayano, S.; Masuda, T. (1999). "Living Polymerization of [o-(Trifluoromethyl)phenyl]acetylene by WOCl4-Based Catalysts such as WOCl4-n-Bu4Sn-t-BuOH (1:1:1)". Macromolecules. 32: 7344–7348. doi:10.1002/zaac.19663440306.


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