Tungsten(VI) oxytetrachloride

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Tungsten(VI) oxytetrachloride
WOCl4.png
WOCl4.jpg
Names
Other names
Tungsten(VI) tetrachloride oxide
Identifiers
3D model (JSmol)
ChemSpider
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EC Number
  • 236-863-7
PubChem CID
  • InChI=1S/4ClH.O.W/h4*1H;;/q;;;;;+4/p-4
    Key: LQNAFXBTXJHEAX-UHFFFAOYSA-J
  • O=[W](Cl)(Cl)(Cl)Cl
Properties
WOCl4
Molar mass 341.651 g/mol
Appearancered 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
GHS labelling: [1]
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
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).
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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 crystalline compound is soluble in nonpolar solvents but it reacts with alcohols and water and forms adducts with Lewis bases.[ citation needed ][ clarification needed ]

Contents

Structure

Structure of solid
WOCl4, illustrating its polymeric structure with short W[?]O and weak W---O bonds in the chains.

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Oxygen, O;
Chlorine, Cl;
Tungsten, W WOCl4crystal.png
Structure of solid WOCl4, illustrating its polymeric structure with short WO and weak W---O bonds in the chains.
  Oxygen, O;   Chlorine, Cl;   Tungsten, W

The solid consists of weakly associated square pyramidal monomers. [2] The compound is classified as an oxyhalide.

Synthesis and reactions

WOCl4 is prepared from tungsten trioxide or hexachloride: [3]

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 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. 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.
  3. Nielson, A. J. (2007). "Tungsten and Molybdenum Tetrachloride Oxides". Inorganic Syntheses. Vol. 23. pp. 195–198. doi:10.1002/9780470132548.ch41. ISBN   9780470132548.
  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.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  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.