Tungsten hexachloride

α-Tungsten hexachloride

β-Tungsten hexachloride

| Tungsten hexachloride | 3D view

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Names
IUPAC names

Tungsten hexachloride
Tungsten(VI) chloride

Identifiers

CAS Number

* 13283-01-7 Y

3D model (JSmol)

* Interactive image

ECHA InfoCard | 100.032.980
EC Number |

* 236-293-9

PubChem CID

* 83301

RTECS number |

* YO7710000

UNII |

* L32HZV95ZE Y

CompTox Dashboard (EPA)

* DTXSID40893933

InChI

* InChI=1S/6ClH.W/h6*1H;/q;;;;;;+6/p-6

SMILES

* Cl[W](Cl)(Cl)(Cl)(Cl)Cl

Properties

Chemical formula

| WCl6
Molar mass | 396.54 g·mol−1
Appearance  | dark blue crystals, moisture sensitive
Density | 3.52 g/cm3
Melting point | 275 °C (527 °F; 548 K)
Boiling point | 346.7 °C (656.1 °F; 619.8 K)

Solubility in water

| Hydrolyzes
Solubility in chlorocarbons  | soluble

Magnetic susceptibility (χ)

| −71.0·10−6 cm3/mol
Structure

Crystal structure

| α:rhombohedral, β: hexagonal

Coordination geometry

| Octahedral

Dipole moment

| 0 D
Hazards
Occupational safety and health (OHS/OSH):

Main hazards

| oxidizer; hydrolysis releases HCl
Related compounds

Other anions

* Tungsten hexafluoride
* Tungsten hexabromide

Other cations

* Molybdenum(VI) chloride
* Uranium hexachloride

Related compounds

* Tungsten(VI) oxytetrachloride
* Tungsten dichloride dioxide
* Tungsten(V) chloride
* Tungsten(IV) chloride
* Tungsten(III) chloride
* Tungsten(II) chloride
* Molybdenum(V) chloride
* Chromyl chloride

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

Chemical compound

Tungsten hexachloride is an inorganic chemical compound of tungsten and chlorine with the chemical formula WCl6. This dark violet-blue compound exists as volatile crystals under standard conditions. It is an important starting reagent in the preparation of tungsten compounds.[1] Other examples of charge-neutral hexachlorides are rhenium(VI) chloride and molybdenum(VI) chloride. The highly volatile tungsten hexafluoride is also known.

As a d0 atom, tungsten hexachloride is diamagnetic.

## Preparation and structure

[edit]

Tungsten hexachloride can be prepared by chlorinating tungsten metal in a sealed tube at 600 °C:[2]

W + 3 Cl2 → WCl6

Tungsten hexachloride exists in both blue and red polymorphs, referred to respectively as α and β. The wine-red β can be obtained by rapid cooling, whereas the blue α form is more stable at room temperature. Although these polymorphs are distinctly colored, their molecular structures are very similar. Both polymorphs feature WCl6 molecules that have octahedral geometry, in which all six W–Cl bonds are equivalent, and their length is equal to 224–226 pm. The densities are very similar: 3.68 g/cm3 for α and 3.62 g/cm3 for β. The low-temperature form is slightly more dense, as expected.[3]

## Reactions

[edit]

Tungsten hexachloride is readily hydrolyzed, even by moist air, giving the orange oxychlorides WOCl4 and WO2Cl2, and subsequently, tungsten trioxide. WCl6 is soluble in carbon disulfide, carbon tetrachloride, and phosphorus oxychloride.[2]

Methylation with trimethylaluminium affords hexamethyl tungsten:

WCl6 \+ 3 Al2(CH3)6 → W(CH3)6 \+ 3 Al2(CH3)4Cl2

Treatment with butyl lithium affords a reagent that is useful for deoxygenation of epoxides.[4]

The chloride ligands in WCl6 can be replaced by many anionic ligands including: bromide, thiocyanate, alkoxide, alkyl and aryl.

Reduction of WCl6 can be effected with a mixture of tetrachloroethylene and tetraphenylarsonium chloride:[5]

2 WCl6 \+ Cl2C=CCl2 \+ 2 (C6H5)4AsCl → 2 (C6H5)4As[WCl6] + Cl3C−CCl3

The W(V) hexachloride is a derivative of tungsten(V) chloride.

It reacts with arsenic or hydrogen arsenide to form tungsten arsenide.[6][7]

## Safety considerations

[edit]

WCl6 is an aggressively corrosive oxidant, and hydrolyzes to release hydrogen chloride.

## References

[edit]

1. ^ J. W. Herndon; M. E. Jung (2007). "Tungsten(VI) Chloride". Encyclopedia of Reagents for Organic Synthesis. Wiley. doi:10.1002/9780470842898.rt430.pub2. ISBN 978-0-471-93623-7..
2. ^ a b M. H. Lietzke; M. L. Holt (1950). "Tungsten(VI) Chloride (Tungsten Hexachloride)". Inorganic Syntheses. Vol. 3\. p. 163\. doi:10.1002/9780470132340.ch44. ISBN 978-0-470-13162-6. `{{cite book}}`: ISBN / Date incompatibility (help)
3. ^ J. C. Taylor; P. W. Wilson (1974). "The Structure of β-Tungsten Hexachloride by Powder Neutron and X-ray Diffraction". Acta Crystallographica. B30 (5): 1216–1220\. Bibcode:1974AcCrB..30.1216T. doi:10.1107/S0567740874004572..
4. ^ M. A. Umbreit, K. B. Sharpless (1990). "Deoxygenation of Epoxides with Lower Valent Tungsten Halides: trans-Cyclododecene". Organic Syntheses; Collected Volumes, vol. 7, p. 121.
5. ^ Uhl, G.; Hey, E.; Becker, G.; Weller, F.; Dehnicke, K. (1983). "Über die Reaktion von 2,2-Dimethylpropylidinphosphan mit Wolframhexachlorid; die Kristallstrukturen von [(Cl3PO)WCL4(H9C4CCC4H9)] und [(H5C6)4As][WCL6]". Zeitschrift für Anorganische und Allgemeine Chemie. 497 (2): 213–223\. doi:10.1002/zaac.19834970221.
6. ^ Lassner, Erik; Schubert, Wolf-Dieter (2012-12-06). Tungsten. Springer Science & Business Media. p. 145\. ISBN 978-1-4615-4907-9.
7. ^ Meyer, R. J. (2013-09-03). Wolfram (in German). Springer-Verlag. p. 207\. ISBN 978-3-662-13401-6.

* v
* t
* e

Tungsten compounds

Tungsten(0)|

* W(CO)6
* W(PMe3)6

Tungsten(II)|

* WSi2
* WCl2
* WI2
* W(OH)2
* W2(hpp)4

Tungsten(III)|

* W2O3
* WCl3
* WI3
* W2(OtBu)6

Tungsten(IV)|

* WC
* WO2
* WS2
* WSe2
* WTe2
* WF4
* WCl4
* WBr4
* WI4

Tungsten(V)|

* W2O5
* WBr5
* W2Cl10
* LiWF6

Tungsten(VI)|

* WO2Cl2
* WBr6
* WCl6
* WF6
* WN2
* WO3
* WS3
* WAs2
* WOBr4
* WOCl4
* WOF4
* H2WO4

| Organotungsten(VI) compounds|

* W(CH3)6

|

Polytungstate salts|

* H3PW12O40
* (NH4)10(H2W12O42)
* Na6[H2W12O40]

* v
* t
* e

Salts and covalent derivatives of the chloride ion

| HCl |  |  |  | He

|
|
|
|

LiCl | BeCl2 | B4Cl4
B12Cl12
BCl3
B2Cl4
+BO3 | C2Cl2
C2Cl4
C2Cl6
CCl4

+CO3 | NCl3
ClN3

+NO3 | ClxOy
Cl2O
Cl2O2
ClO
ClO2
Cl2O4
Cl2O6
Cl2O7
ClO4
+O | ClF
ClF3
ClF5 | Ne
NaCl | MgCl2 | AlCl
AlCl3 | Si5Cl12
Si2Cl6
SiCl4 | P2Cl4
PCl3
PCl5
+P | S2Cl2
SCl2
SCl4
+SO4 | Cl2 | Ar
KCl | CaCl
CaCl2 |  | ScCl3 | TiCl2
TiCl3
TiCl4 | VCl2
VCl3
VCl4
VCl5 | CrCl2
CrCl3
CrCl4 | MnCl2
MnCl3 | FeCl2
FeCl3 | CoCl2
CoCl3 | NiCl2 | CuCl
CuCl2 | ZnCl2 | GaCl
GaCl3 | GeCl2
GeCl4 | AsCl3
AsCl5
+As | Se2Cl2
SeCl2
SeCl4 | BrCl | Kr
RbCl | SrCl2 |  | YCl3 | ZrCl2
ZrCl3
ZrCl4 | NbCl3
NbCl4
NbCl5 | MoCl2
MoCl3
MoCl4
MoCl5
MoCl6 | TcCl3
TcCl4 | RuCl2
RuCl3
RuCl4 | RhCl3 | PdCl2 | AgCl | CdCl2 | InCl
InCl2
InCl3 | SnCl2
SnCl4 | SbCl3
SbCl5 | Te3Cl2
TeCl2
TeCl4 | ICl
ICl3 | XeCl
XeCl2
XeCl4
CsCl | BaCl2 | *  | LuCl3 | HfCl4 | TaCl3
TaCl4
TaCl5 | WCl2
WCl3
WCl4
WCl5
WCl6 | ReCl3
ReCl4
ReCl5
ReCl6 | OsCl2
OsCl3
OsCl4
OsCl5 | IrCl2
IrCl3
IrCl4 | PtCl2
PtCl4 | AuCl
(Au[AuCl4])2
AuCl3 | Hg2Cl2
HgCl2 | TlCl
TlCl3 | PbCl2
PbCl4 | BiCl3 | PoCl2
PoCl4 | AtCl | Rn
FrCl | RaCl2 | **  | LrCl3 | RfCl4 | DbCl5 | SgO2Cl2 | BhO3Cl | Hs  | Mt  | Ds  | Rg  | Cn  | Nh  | Fl  | Mc  | Lv  | Ts  | Og

*  | LaCl3 | CeCl3 | PrCl3 | NdCl2
NdCl3 | PmCl3 | SmCl2
SmCl3 | EuCl2
EuCl3 | GdCl3 | TbCl3 | DyCl2
DyCl3 | HoCl3 | ErCl3 | TmCl2
TmCl3 | YbCl2
YbCl3
**  | AcCl3 | ThCl3
ThCl4 | PaCl4
PaCl5 | UCl3
UCl4
UCl5
UCl6 | NpCl3
NpCl4 | PuCl3 | AmCl2
AmCl3 | CmCl3 | BkCl3 | CfCl3
CfCl2 | EsCl2
EsCl3 | FmCl2 | MdCl2 | NoCl2
*[CID]: Compound ID
*[EPA]: U.S. Environmental Protection Agency
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