Tungsten dichloride dioxide

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Tungsten dichloride dioxide
Tungsten(VI) dioxydichloride WO2Cl2distances.png
Tungsten(VI) dioxydichloride
Names
IUPAC name
Tungsten(VI) dichloride dioxide
Other names
  • Tungsten(VI) dioxydichloride
  • Tungsten dichloride dioxide
  • Tungstyl chloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.496 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 236-862-1
PubChem CID
  • InChI=1S/2ClH.2O.W/h2*1H;;;/q;;2*-2;/p-2
    Key: DVBXMVWZPVBSJY-UHFFFAOYSA-L
  • InChI=1S/2ClH.2O.W/h2*1H;;;/q;;2*-2;/p-2
  • [O-2].[O-2].[Cl-].[Cl-].[W]
Properties
WO2Cl2
Molar mass 286.74 g·mol−1
AppearanceYellow-red crystals
Density 4.67 g/cm3
Melting point 265 °C (509 °F; 538 K)
Boiling point Sublimes at > 350 °C in vacuum
decomposes
Solubility slightly soluble in ethanol
Structure
orthorhombic
Hazards
GHS labelling: [1]
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
Related compounds
Other anions
Other cations
Related compounds
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 dichloride dioxide, or tungstyl chloride is the chemical compound with the formula W O 2 Cl 2. It is a yellow solid. It is used as a precursor to other tungsten compounds. Like other tungsten halides, WO2Cl2 is sensitive to moisture, undergoing hydrolysis.

Contents

Preparation

WO2Cl2 is prepared by ligand redistribution reaction from tungsten trioxide and tungsten hexachloride:

2 WO3 + WCl6 → 3 WO2Cl2

Using a two-zone tube furnace, a vacuum-sealed tube containing these solids is heated to 350 °C. The yellow product sublimes to the cooler end of the reaction tube. No redox occurs in this process. [2] An alternative route highlights the oxophilicity of tungsten: [3]

WCl6 + 2 ((CH3)3Si)2O → 3 WO2Cl2 + 4 (CH3)3SiCl

This reaction, like the preceding one, proceeds via the intermediacy of WOCl4.

Structure

Gaseous tungsten dichloride dioxide is a monomer. [4] Solid tungsten dichloride dioxide is a polymer consisting of distorted octahedral W centres. The polymer is characterized by two short W-O distances, typical for a multiple W-O bond, and two long W-O distances more typical of a single or dative W-O bond. [5]

Tungsten forms a number of oxyhalides including WOCl4, WOCl3, WOCl2. The corresponding bromides (WOBr4, WOBr3, WOBr2) are also known as is WO2I2. [6]

Reactions

Structure of the complex WO2Cl2(dimethoxyethane). WO2Cl2(dme).png
Structure of the complex WO2Cl2(dimethoxyethane).

WO2Cl2 is a Lewis acid, forming soluble adducts of the type WO2Cl2L2, where L is a donor ligand such as bipyridine and dimethoxyethane. Such complexes often cannot be prepared by depolymerization of the inorganic solid, but are generated in situ from WOCl4. [7]

References

  1. ↑ "C&L Inventory". echa.europa.eu. Retrieved 12 December 2021.
  2. ↑ Tillack, J. (1973). "Tungsten Oxyhalides". Inorganic Syntheses. Vol. 14. pp. 109–122. doi:10.1002/9780470132456.ch22. ISBN   9780470132456.{{cite book}}: |journal= ignored (help)
  3. ↑ Gibson, V. C.; Kee, T. P.; Shaw, A. (1988). "New, improved synthesis of the group 6 oxyhalides, W(O)Cl4, W(O)2Cl2 and Mo(O)2Cl2". Polyhedron . 7 (7): 579–80. doi:10.1016/S0277-5387(00)86336-6.
  4. ↑ Ward, Brian G.; Stafford, Fred E. (1968). "Synthesis and Structure of Four- and Five-Coordinated Gaseous Oxohalides of Molybdenum(VI) and Tungsten(VI)". Inorganic Chemistry. 7 (12): 2569–2573. doi:10.1021/ic50070a020.
  5. ↑ Jarchow, O.; Schröder, F.; Schulz, H. "Kristallstruktur und Polytypie von WO2Cl2" Zeitschrift für anorganische und allgemeine Chemie 1968, vol. 363, p. 345ff. doi : 10.1002/zaac.19683630108
  6. ↑ Holleman, A. F.; Wiberg, E. Inorganic Chemistry Academic Press: San Diego, 2001. ISBN   0-12-352651-5.
  7. ↑ K. Dreisch, C. Andersson, C. Stalhandske "Synthesis and structure of dimethoxyethane-dichlorodioxo-tungsten(VI)—a highly soluble derivative of tungsten dioxodichloride" Polyhedron 1991, volume 10, p. 2417. doi : 10.1016/S0277-5387(00)86203-8
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