Tungsten hexachloride: Difference between revisions
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| verifiedrevid = 353530744 |
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|verifiedrevid = 448559102 |
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| Name = Tungsten hexachloride |
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|Name = Tungsten hexachloride |
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| ImageFile = Hexachlorotungsten.svg |
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|ImageFile = Tungsten(VI) Chloride.jpg |
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<!-- | ImageSize = 150px --> |
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|ImageCaption = α-Tungsten hexachloride |
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|ImageFile1 = Β-tungsten hexachloride.png |
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|ImageCaption1 = β-Tungsten hexachloride |
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| OtherNames = |
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|ImageFileL2 = Hexachlorotungsten.svg |
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| Section1 = {{Chembox Identifiers |
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|ImageSizeL2 = 115px |
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| CASNo = 13283-01-7 |
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|ImageNameL2 = Tungsten hexachloride |
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| CASNo_Ref = {{cascite}} |
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|ImageFileR2 = Tungsten-hexachloride-from-xtal-3D-balls.png |
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| PubChem = 83301 |
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|ImageSizeR2 = 100px |
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| RTECS = YO7710000 |
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|ImageNameR2 = 3D view |
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}} |
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|IUPACName = Tungsten hexachloride<br/>Tungsten(VI) chloride |
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| Section2 = {{Chembox Properties |
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|Section1 = {{Chembox Identifiers |
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| Formula = Cl<sub>6</sub>W |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| MolarMass = 396.61 g/mol |
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|CASNo = 13283-01-7 |
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| Appearance = dark blue crystals, moisture sensitive |
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|UNII_Ref = {{fdacite|correct|FDA}} |
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| Density = 3.52 g/cm<sup>3</sup> |
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|UNII = L32HZV95ZE |
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| Solubility = hydrolyzes |
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|PubChem = 83301 |
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| Solvent = chlorocarbons |
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|RTECS = YO7710000 |
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| SolubleOther = soluble |
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|EINECS = 236-293-9 |
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| MeltingPt = 275 °C |
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|InChI = 1S/6ClH.W/h6*1H;/q;;;;;;+6/p-6 |
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| BoilingPt = 346.7 °C |
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|SMILES = Cl[W](Cl)(Cl)(Cl)(Cl)Cl |
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}} |
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| Section3 = {{Chembox Structure |
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| Coordination = octahedral |
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| CrystalStruct = α:rhombohedral, β: hexagonal |
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| Dipole = 0 [[Debye|D]] |
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}} |
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| Section7 = {{Chembox Hazards |
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| ExternalMSDS = |
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| EUIndex = Not listed |
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| MainHazards = oxidizer; hydrolysis releases HCl |
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| RPhrases = |
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| SPhrases = |
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}} |
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| Section8 = {{Chembox Related |
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| OtherAnions = [[Tungsten hexafluoride]]<br/>[[Tungsten hexabromide]] |
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| OtherCations = [[Molybdenum(V) chloride]]<br/>[[Chromyl chloride]] |
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}} |
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}} |
}} |
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|Section2 = {{Chembox Properties |
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|Formula = {{chem2|WCl6}} |
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|W=1|Cl=6 |
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|Appearance = dark blue crystals, moisture sensitive |
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|Density = 3.52 g/cm<sup>3</sup> |
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|Solubility = [[Hydrolyzes]] |
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|Solvent = chlorocarbons |
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|SolubleOther = soluble |
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|MeltingPtC = 275 |
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|BoilingPtC = 346.7 |
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|MagSus = −71.0·10<sup>−6</sup> cm<sup>3</sup>/mol}} |
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|Section3 = {{Chembox Structure |
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|Coordination = [[Octahedral molecular geometry|Octahedral]] |
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|CrystalStruct = α:rhombohedral, β: hexagonal |
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|Dipole = 0 [[Debye|D]] |
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}} |
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|Section4 = {{Chembox Hazards |
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|MainHazards = oxidizer; hydrolysis releases HCl |
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}} |
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|Section5 = {{Chembox Related |
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|OtherAnions = {{ubl|[[Tungsten hexafluoride]]|[[Tungsten hexabromide]]}} |
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|OtherCompounds = {{ubl|[[Tungsten(IV) chloride]]|[[Tungsten(V) chloride]]|[[Molybdenum(V) chloride]]|[[Chromyl chloride]]}} |
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}} |
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}} |
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{{Use American English|date=May 2024}} |
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'''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}}. |
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</ref> Other examples of charge-neutral hexachlorides are [[rhenium(VI) chloride]] and [[molybdenum(VI) chloride]]. The highly volatile [[tungsten hexafluoride]] is also known. |
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As a [[d electron count#Possible d electron counts|d<sup>0</sup>]] atom, tungsten hexachloride is [[diamagnetic]]. |
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'''Tungsten hexachloride''' is the [[chemical compound]] of [[tungsten]] and [[chlorine]] with the [[chemical formula|formula]] WCl<sub>6</sub>. This dark violet blue species exists as a volatile solid under standard conditions. It is an important starting reagent in the preparation of tungsten compounds.<ref>J. W. Herndon "Tungsten(VI) Chloride” in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289. |
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</ref> Cl<sub>6</sub>W is a rare example of a charge-neutral hexachloride, another example being ReCl<sub>6</sub>. Better known than Cl<sub>6</sub>W is the still more volatile [[tungsten hexafluoride|F<sub>6</sub>W]]. |
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==Preparation and structure== |
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As a d<sup>0</sup> ion, W(VI) forms [[diamagnetic]] derivatives. The hexachloride is [[octahedral molecular geometry|octahedral]] with equivalent W-Cl distances of 2.24 - 2.26 Å.<ref>J. C. Taylor and P. W. Wilson "The structure of [beta]-tungsten hexachloride by powder neutron and X-ray diffraction" Acta Crystallographic (1974). B30, 1216-1220.doi:10.1107/S0567740874004572.</ref> In Cl<sub>6</sub>W, the chloride [[ligand]]s are donors in both sigma- and pi sense<!-- explain|Does this refer to Molecular Orbitals? |
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Tungsten hexachloride can be prepared by chlorinating tungsten metal in a sealed tube at 600 °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> |
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:{{chem2|W + 3 Cl2 → WCl6}} |
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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 geometry]], 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/cm<sup>3</sup> for α and 3.62 g/cm<sup>3</sup> 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> |
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NOTE - this was originally an instance of the "Explain" template, but it was just too messy. So I commented it out. Feel free to remove this bulky comment if you can properly answer the question. |
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==Reactions== |
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-->.{{Fact|date=November 2008}} Methylation with [[trimethylaluminium]] affords [[hexamethyl tungsten]]. 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> |
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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" /> |
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[[Methylation]] with [[trimethylaluminium]] affords [[hexamethyl tungsten]]: |
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The chloride ligands in Cl<sub>6</sub>W can be replaced by many anionic ligands including [[bromide|Br<sup>−</sup>]], [[thiocyanate|NCS<sup>−</sup>]], and [[alkoxide|RO<sup>−</sup>]] (R = alkyl, aryl). |
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:{{chem2|WCl6 + 3 Al2(CH3)6 → W(CH3)6 + 3 Al2(CH3)4Cl2}} |
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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> |
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The [[chloride]] [[ligands]] in {{chem2|WCl6}} can be replaced by many [[anionic]] ligands including: [[bromide]], [[thiocyanate]], [[alkoxide]], [[alkyl]] and [[aryl]]). |
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[[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 [(Cl<sub>3</sub>PO)WCL<sub>4</sub>(H<sub>9</sub>C<sub>4</sub>CCC<sub>4</sub>H<sub>9</sub>)] und [(H<sub>5</sub>C<sub>6</sub>)<sub>4</sub>As][WCL<sub>6</sub>] |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> |
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:{{chem2|2 WCl6 + Cl2C\dCCl2 + 2 (C6H5)4AsCl -> 2 (C6H5)4As[WCl6] + Cl3C\sCCl3}} |
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The W(V) hexachloride is a derivative of [[tungsten(V) chloride]]. |
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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> |
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==Safety considerations== |
==Safety considerations== |
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{{chem2|WCl6}} is an aggressively [[corrosive]] [[oxidant]], and hydrolyzes to release [[hydrogen chloride]]. |
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==References== |
==References== |
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{{reflist}} |
{{reflist}} |
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{{Tungsten compounds}} |
{{Tungsten compounds}} |
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{{Chlorides}} |
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[[Category:Tungsten |
[[Category:Tungsten halides]] |
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[[Category:Chlorides]] |
[[Category:Chlorides]] |
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[[Category:Metal halides]] |
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[[Category:Octahedral compounds]] |
[[Category:Octahedral compounds]] |
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[[de:Wolfram(VI)-chlorid]] |
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[[nl:Wolfraam(VI)chloride]] |
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[[pt:Hexacloreto de tungsténio]] |