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'''Tungsten dichloride dioxide''' is the ] with the formula ]]]. This yellow-colored solid is used as a precursor to other tungsten compounds. Like other tungsten halides, WO<sub>2</sub>Cl<sub>2</sub> is sensitive to moisture, undergoing hydrolysis. '''Tungsten dichloride dioxide''' is the ] with the formula ]]]. It is a yellow-colored solid. It is used as a precursor to other tungsten compounds. Like other tungsten halides, WO<sub>2</sub>Cl<sub>2</sub> is sensitive to moisture, undergoing hydrolysis.


==Preparation== ==Preparation==
WO<sub>2</sub>Cl<sub>2</sub> is prepared by ligand redistribution reaction from ] and ]: WO<sub>2</sub>Cl<sub>2</sub> is prepared by ligand redistribution reaction from ] and ]:
: 2 WO<sub>3</sub> + WCl<sub>6</sub> &rarr; 3 WO<sub>2</sub>Cl<sub>2</sub> : 2 WO<sub>3</sub> + WCl<sub>6</sub> &rarr; 3 WO<sub>2</sub>Cl<sub>2</sub>
Using a two-zone 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.<ref>{{cite journal | author = Tillack, J. | title = Tungsten Oxyhalides | journal = ] | year = 1973 | volume = 14 | pages = 109–122 | doi = 10.1002/9780470132456.ch22 }}</ref> An alternative route highlights the ] of tungsten:<ref>{{cite journal | author = Gibson, V. C.; Kee, T. P.; Shaw, A. | title = New, improved synthesis of the group 6 oxyhalides, W(O)Cl<sub>4</sub>, W(O)<sub>2</sub>Cl<sub>2</sub> and Mo(O)<sub>2</sub>Cl<sub>2</sub> | journal = ] | year = 1988 | volume = 7 | issue = 7 | pages = 579–80 | doi = 10.1016/S0277-5387(00)86336-6}}</ref> Using a two-zone ], 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.<ref>{{cite journal | author = Tillack, J. | title = Tungsten Oxyhalides | journal = ] | year = 1973 | volume = 14 | pages = 109–122 | doi = 10.1002/9780470132456.ch22 }}</ref> An alternative route highlights the ] of tungsten:<ref>{{cite journal | author = Gibson, V. C.; Kee, T. P.; Shaw, A. | title = New, improved synthesis of the group 6 oxyhalides, W(O)Cl<sub>4</sub>, W(O)<sub>2</sub>Cl<sub>2</sub> and Mo(O)<sub>2</sub>Cl<sub>2</sub> | journal = ] | year = 1988 | volume = 7 | issue = 7 | pages = 579–80 | doi = 10.1016/S0277-5387(00)86336-6}}</ref>
:WCl<sub>6</sub> + 2 O(Si(CH<sub>3</sub>)<sub>3</sub>)<sub>2</sub> &rarr; 3 WO<sub>2</sub>Cl<sub>2</sub> + 4 ClSi(CH<sub>3</sub>)<sub>3</sub> :WCl<sub>6</sub> + 2 O(Si(CH<sub>3</sub>)<sub>3</sub>)<sub>2</sub> &rarr; 3 WO<sub>2</sub>Cl<sub>2</sub> + 4 ClSi(CH<sub>3</sub>)<sub>3</sub>


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==Structure== ==Structure==
The compound is a polymer consisting of distorted octahedral W centres. The monomer is characterized by two short W-O distances, typical for a double or triple bond, and two long W-O distances more typical of a single W-O bond. The compound is a polymer consisting of distorted octahedral W centres. The monomer 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 datice W-O bond.<ref>Jarchow, O.; Schröder, F.; Schulz, H. "Kristallstruktur und Polytypie von WO<sub>2</sub>Cl<sub>2</sub>" Zeitschrift für anorganische und allgemeine Chemie 1968, vol. 363, p. 345ff. {{DOI|10.1002/zaac.19683630108}}</ref>


==Other tungsten oxy chlorides and related oxy halides== ==Other tungsten oxy chlorides and related oxy halides==
Tungsten forms a number of oxyhalides including ], WOCl<sub>3</sub>, WOCl<sub>2</sub>. The corresponding bromides (WOBr<sub>4</sub>, WOBr<sub>3</sub>, WOBr<sub>2</sub>) are also known as is WO<sub>2</sub>I<sub>2</sub>.<ref>Holleman, A. F.; Wiberg, E. ''Inorganic Chemistry'' Academic Press: San Diego, 2001. ISBN 0-12-352651-5.</ref> Tungsten forms a number of oxyhalides including ], WOCl<sub>3</sub>, WOCl<sub>2</sub>. The corresponding bromides (WOBr<sub>4</sub>, WOBr<sub>3</sub>, WOBr<sub>2</sub>) are also known as is WO<sub>2</sub>I<sub>2</sub>.<ref>Holleman, A. F.; Wiberg, E. ''Inorganic Chemistry'' Academic Press: San Diego, 2001. ISBN 0-12-352651-5.</ref>
] ]).]]
==Reactions== ==Reactions==
WO<sub>2</sub>Cl<sub>2</sub> is a ], forming soluble adducts of the type WO<sub>2</sub>Cl<sub>2</sub>L<sub>2</sub>, where L is a donor ligand such as ] and ]. Such complexes often cannot be prepared by depolymerization of the inorganic solid, but are generated from WOCl<sub>4</sub>. WO<sub>2</sub>Cl<sub>2</sub> is a ], forming soluble adducts of the type WO<sub>2</sub>Cl<sub>2</sub>L<sub>2</sub>, where L is a donor ligand such as ] and ]. Such complexes often cannot be prepared by depolymerization of the inorganic solid, but are generated in situ from WOCl<sub>4</sub>.<ref>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}}</ref>


==References== ==References==

Revision as of 23:14, 18 June 2014

Tungsten(VI) dioxydichloride
Tungsten(VI) dioxydichloride
Names
Other names tungsten(VI) dioxydichloride
Identifiers
CAS Number
3D model (JSmol)
ECHA InfoCard 100.033.496 Edit this at Wikidata
EC Number
  • 236-862-1
PubChem CID
CompTox Dashboard (EPA)
InChI
  • InChI=1S/2ClH.2O.W/h2*1H;;;/q;;2*-2;/p-2
SMILES
  • ....
Properties
Chemical formula WO2Cl2
Molar mass 286.749 g/mol
Appearance yellow crystals
Density 4.67 g/cm, solid
Melting point 265 °C (509 °F; 538 K)
Boiling point sublimes > 350 °C in vacuo
Solubility in water decomposes
Structure
Crystal structure orthorhombic
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

Tungsten dichloride dioxide is the chemical compound with the formula WO2Cl2. It is a yellow-colored solid. It is used as a precursor to other tungsten compounds. Like other tungsten halides, WO2Cl2 is sensitive to moisture, undergoing hydrolysis.

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. An alternative route highlights the oxophilicity of tungsten:

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

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

Structure

The compound is a polymer consisting of distorted octahedral W centres. The monomer 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 datice W-O bond.

Other tungsten oxy chlorides and related oxy halides

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

Structure of the complex WO2Cl2(dimethoxyethane).

Reactions

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.

References

  1. Tillack, J. (1973). "Tungsten Oxyhalides". Inorg. Synth. 14: 109–122. doi:10.1002/9780470132456.ch22.
  2. 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.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  3. 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
  4. Holleman, A. F.; Wiberg, E. Inorganic Chemistry Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  5. 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
Tungsten compounds
Tungsten(0)
Tungsten(II)
Tungsten(III)
Tungsten(IV)
Tungsten(V)
Tungsten(VI)
Organotungsten(VI) compounds
Polytungstate salts


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