Tungsten hexachloride: Difference between revisions

|Watchedfields = changed

|verifiedrevid = 448559102

|Name = Tungsten hexachloride

|ImageFile = Tungsten(VI) Chloride.jpg

| = Tungsten hexachloride

| = hexachloride

|ImageCaption1 = β-Tungsten hexachloride

|ImageFileL2 = Hexachlorotungsten.svg

|ImageSizeL2 = 115px

|ImageNameL2 = Tungsten hexachloride

|ImageFileR2 = Tungsten-hexachloride-from-xtal-3D-balls.png

|ImageSizeR2 = 100px

|ImageNameR2 = 3D view

|IUPACName = Tungsten hexachloride<br/>Tungsten(VI) chloride

|Section1 = {{Chembox Identifiers

|CASNo_Ref = {{cascite|correct|CAS}}

|CASNo = 13283-01-7

|UNII_Ref = {{fdacite|correct|FDA}}

|UNII = L32HZV95ZE

|PubChem = 83301

|RTECS = YO7710000

|EINECS = 236-293-9

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

|SMILES = Cl[W](Cl)(Cl)(Cl)(Cl)Cl

|Section2 = {{Chembox Properties

|Formula = {{chem2|WCl6}}

|W=1|Cl=6

|Appearance = dark blue crystals, moisture sensitive

|Density = 3.52 g/cm³

|Solubility = [[Hydrolyzes]]

|Solvent = chlorocarbons

|SolubleOther = soluble

|MeltingPtC = 275

|BoilingPtC = 346.7

|MagSus = −71.0·10⁻⁶ cm³/mol}}

|Section3 = {{Chembox Structure

|Coordination = [[Octahedral molecular geometry|Octahedral]]

|CrystalStruct = α:rhombohedral, β: hexagonal

|Dipole = 0 [[Debye|D]]

}}

|Section4 = {{Chembox Hazards

|MainHazards = oxidizer; hydrolysis releases HCl

}}

|Section5 = {{Chembox Related

|OtherAnions = {{ubl|[[Tungsten hexafluoride]]|[[Tungsten hexabromide]]}}

|OtherCompounds = {{ubl|[[Tungsten(IV) chloride]]|[[Tungsten(V) chloride]]|[[Molybdenum(V) chloride]]|[[Chromyl chloride]]}}

}}

}}

{{Use American English|date=May 2024}}

'''Tungsten hexachloride''' is an [[inorganic chemical compound]] of [[tungsten]] and [[chlorine]] with the [[chemical formula]] {{chem2|WCl6|auto=1}}. This dark violet-blue compound exists as [[Volatility (chemistry)|volatile]] crystals under [[standard conditions]]. It is an important starting reagent in the preparation of tungsten compounds.<ref>{{cite encyclopedia|author1=J. W. Herndon|author2=M. E. Jung|title=Encyclopedia of Reagents for Organic Synthesis|chapter=Tungsten(VI) Chloride |year=2007|publisher=Wiley|doi=10.1002/9780470842898.rt430.pub2|isbn=978-0-471-93623-7}}.

</ref> Other examples of charge-neutral hexachlorides are [[rhenium(VI) chloride]] and [[molybdenum(VI) chloride]]. The highly volatile [[tungsten hexafluoride]] is also known.

As a [[d electron count#Possible d electron counts|d⁰]] atom, tungsten hexachloride is [[diamagnetic]].

==Preparation and structure==

Tungsten hexachloride can be prepared by chlorinating tungsten metal in a sealed tube at 600&nbsp;°C:<ref name="InorgSyn">{{cite book| title= Inorganic Syntheses| author1 = M. H. Lietzke| author2 = M. L. Holt| chapter= Tungsten(VI) Chloride (Tungsten Hexachloride)| volume = 3| year = 1950| doi = 10.1002/9780470132340.ch44 | page = 163| isbn= 978-0-470-13162-6}}</ref>

:{{chem2|W + 3 Cl2 → WCl6}}

Tungsten hexachloride exists in both blue and red [[polymorphism (materials science)|polymorph]]s, 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 {{chem2|WCl6|auto=1}} molecules that have [[octahedral molecular geometry|octahedral]], in which all six W–Cl bonds are equivalent, and their length is equal to 224–226 [[Picometre|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.<ref>{{cite journal |author1=J. C. Taylor |author2=P. W. Wilson |title=The Structure of β-Tungsten Hexachloride by Powder Neutron and X-ray Diffraction |journal=Acta Crystallographica |year=1974 |volume=B30 |issue=5 |pages=1216–1220 |doi=10.1107/S0567740874004572 |doi-access=free|bibcode=1974AcCrB..30.1216T }}.</ref>

==Reactions==

Tungsten hexachloride is readily [[hydrolyzed]], even by [[Moisture|moist]] [[air]], giving the orange [[oxychloride]]s [[Tungsten(VI) oxytetrachloride|{{chem2|WOCl4}}]] and [[Tungsten dichloride dioxide|{{chem2|WO2Cl2}}]], and subsequently, [[tungsten trioxide]]. {{chem2|WCl6}} is soluble in [[carbon disulfide]], [[carbon tetrachloride]], and [[phosphorus oxychloride]].<ref name="InorgSyn" />

[[Methylation]] with [[trimethylaluminium]] affords [[hexamethyl tungsten]]:

:{{chem2|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 [[epoxide]]s.<ref>{{OrgSynth | author = M. A. Umbreit, K. B. Sharpless | title = Deoxygenation of Epoxides with Lower Valent Tungsten Halides: trans-Cyclododecene | collvol = 7 | collvolpages = 121| year = 1990 | prep = CV7P0121}}</ref>

The [[chloride]] [[ligands]] in {{chem2|WCl6}} can be replaced by many [[anionic]] ligands including: [[bromide]], [[thiocyanate]], [[alkoxide]], [[alkyl]] and [[aryl]]).

[[Redox|Reduction]] of {{chem2|WCl6}} can be effected with a mixture of [[tetrachloroethylene]] and [[tetraphenylarsonium chloride]]:<ref>{{cite journal |doi=10.1002/zaac.19834970221 |title=Über die Reaktion von 2,2-Dimethylpropylidinphosphan mit Wolframhexachlorid; die Kristallstrukturen von &#91;(Cl₃PO)WCL₄(H₉C₄CCC₄H₉)&#93; und &#91;(H₅C₆)₄As&#93;&#91;WCL₆&#93; |year=1983 |last1=Uhl |first1=G. |last2=Hey |first2=E. |last3=Becker |first3=G. |last4=Weller |first4=F. |last5=Dehnicke |first5=K. |journal=Zeitschrift für Anorganische und Allgemeine Chemie |volume=497 |issue=2 |pages=213–223 |url=http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-57717 }}</ref>

:{{chem2|2 WCl6 + Cl2C\dCCl2 + 2 (C6H5)4AsCl -> 2 (C6H5)4As[WCl6] + Cl3C\sCCl3}}

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

It reacts with [[arsenic]] or [[hydrogen arsenide]] to form [[tungsten arsenide]].<ref>{{cite book | last1=Lassner | first1=Erik | last2=Schubert | first2=Wolf-Dieter | title=Tungsten | publisher=Springer Science & Business Media | date=2012-12-06 | isbn=978-1-4615-4907-9|page=145}}</ref><ref>{{cite book | last=Meyer | first=R. J. | title=Wolfram | publisher=Springer-Verlag | date=2013-09-03 | isbn=978-3-662-13401-6 | language=de|page=207}}</ref>

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

{{Chlorides}}

[[Category:Tungsten ]]