Tungsten(VI) oxytetrachloride

Tungsten(VI) oxytetrachloride
Names
	Other names Tungsten(IV) chloride oxide
Identifiers
CAS Number	13520-78-0 ;
3D model (JSmol)	Interactive image;
ECHA InfoCard	100.033.497
PubChem CID	19596810;
	InChI InChI=1S/4ClH.O.W/h4*1H;;/q;;;;;+4/p-4;
	SMILES O=[W](Cl)(Cl)(Cl)Cl;
Properties
Chemical formula	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)
Solubility in water	reacts
Solubility	soluble in benzene and CS2
Hazards
EU classification (DSD) (outdated)	not listed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

Tungsten(VI) oxytetrachloride is the inorganic compound with the formula W O Cl₄. 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.

Structure

Structure of solid WOCl₄, illustrating its polymeric structure with short W≡O 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

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.
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.
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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[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.