Tungsten(VI) oxytetrachloride

Tungsten(VI) oxytetrachloride

Names
Other names Tungsten(VI) tetrachloride oxide
Identifiers
CAS Number	13520-78-0  Y
3D model (JSmol)	Interactive image
ChemSpider	21171360
ECHA InfoCard	100.033.497
EC Number	236-863-7
PubChem CID	19596810
InChI InChI=1S/4ClH.O.W/h4*1H;;/q;;;;;+4/p-4 Key: LQNAFXBTXJHEAX-UHFFFAOYSA-J
SMILES O=[W](Cl)(Cl)(Cl)Cl
Properties
Chemical formula	WOCl4
Molar mass	341.651 g/mol
Appearance	Orange-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
GHS labelling: [1]
Pictograms
Signal word	Warning
Hazard statements	H315, H319, H335
Precautionary statements	P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
Related compounds
Other anions	Tungsten(VI) oxytetrafluoride Tungsten(VI) oxytetrabromide
Other cations	Molybdenum oxytetrachloride
Related compounds	Tungsten dichloride dioxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Y  verify  (what is  YN ?) Infobox references

Tungsten(VI) oxytetrachloride is the inorganic compound with the formula W O Cl ₄. This diamagnetic solid is used to prepare other complexes of tungsten. The red-orange solid that is soluble in aromatic and chlorinated solvents. It reacts with alcohols and water. ^[2]

Structure

Structure of solid WOCl₄, illustrating its polymeric structure with short W≡O and weak W---O bonds in the chains.
  Oxygen, O;   Chlorine, Cl;   Tungsten, W

The solid consists of weakly associated square pyramidal monomers. ^[3] The compound is classified as an oxyhalide.

Synthesis and reactions

WOCl₄ is prepared from tungsten trioxide or hexachloride: ^[2]

WO₃ + 2 SOCl₂ → WOCl₄ + 2 SO₂

WCl₆ + ((CH₃)₃Si)₂O → WOCl₄ + 2 (CH₃)₃SiCl

It is "difficult to prepare by other means," ^[4] but thionyl chloride also oxidizes tungsten(IV) oxide to the oxytetrachloride at 200 °C. ^[5]

WOCl₄ is a Lewis acid. It forms 1:1 adducts with Lewis bases such as acetonitrile and THF. ^[2]

It is a precursor to catalysts used for polymerization of alkynes. ^[6]

References

1. "Tungsten tetrachloride oxide". pubchem.ncbi.nlm.nih.gov. Retrieved 12 December 2021.
2. Nielson, A. J. (2007). "Tungsten and Molybdenum Tetrachloride Oxides". Inorganic Syntheses. Vol. 23. pp. 195–198. doi:10.1002/9780470132548.ch41. ISBN   9780470132548.
3. 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.
4. Audrieth, Ludwig F.; Kleinberg, Jacob (1953). Non-aqueous solvents. New York: John Wiley & Sons. p. 224. LCCN   52-12057.
5. Groh, Matthias F.; Müller, Ulrike; Ahmed, Ejaz; Rothenberger, Alexander; Ruck, Michael (2013) [June 3, 2013]. "Substitution of conventional high-temperature syntheses of inorganic compounds by near-room-temperature syntheses in ionic liquids". Zeitschrift für Naturforschung. 68b (10). Tübingen: Verlag der Zeitschrift für Naturforschung: 1116. doi:10.5560/ZNB.2013-3141.
6. 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.