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Tungsten hexachloride is the chemical compound of tungsten and chlorine with the
formula In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwee ...
WCl6. 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. Other examples of charge-neutral hexachlorides are
rhenium(VI) chloride Rhenium(VI) chloride is the inorganic compound with the formula ReCl6. It is a black paramagnetic solid. The molecules adopt an octahedral structure as seen in tungsten(VI) chloride. Preparation and reactions Rhenium(VI) chloride was first gener ...
and
molybdenum(VI) chloride Molybdenum(VI) chloride is the inorganic compound with the formula MoCl6. It is a black diamagnetic solid. The molecules adopt an octahedral structure as seen in β- tungsten(VI) chloride. Preparation and reactions Molybdenum(VI) chloride is pr ...
. The highly volatile
tungsten hexafluoride Tungsten(VI) fluoride, also known as tungsten hexafluoride, is an inorganic compound with the formula W F6. It is a toxic, corrosive, colorless gas, with a density of about (roughly 11 times heavier than air). It is one of the densest known gase ...
is also known. As a d0 ion, W(VI) forms diamagnetic derivatives. The hexachloride is octahedral with equivalent W–Cl distances of 2.24–2.26 Å.


Preparation

Tungsten hexachloride can be prepared by chlorinating tungsten metal in a sealed tube at 600 °C: : W + 3 Cl2 → WCl6


Properties and Reactions

Tungsten (VI) chloride is a blue-black solid at room temperature. At lower temperatures, it becomes wine-red in color. A red form of the compound can be made by rapidly condensing its vapor, which reverts to the blue-black form on gentle heating. It is readily hydrolyzed, even by moist air, giving the orange
oxychloride In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula , where X = fluorine (F), ...
s WOCl4 and WO2Cl2, and subsequently,
tungsten trioxide Tungsten(VI) oxide, also known as tungsten trioxide is a chemical compound of oxygen and the transition metal tungsten, with formula WO3. The compound is also called tungstic anhydride, reflecting its relation to tungstic acid . It is a light ...
. WCl6 is soluble in carbon disulfide,
carbon tetrachloride Carbon tetrachloride, also known by many other names (such as tetrachloromethane, also IUPAC nomenclature of inorganic chemistry, recognised by the IUPAC, carbon tet in the cleaning industry, Halon-104 in firefighting, and Refrigerant-10 in HVAC ...
, and phosphorus oxychloride. 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. The chloride ligands in WCl6 can be replaced by many anionic ligands including: bromide, thiocyanate and
alkoxide In chemistry, an alkoxide is the conjugate base of an alcohol and therefore consists of an organic group bonded to a negatively charged oxygen atom. They are written as , where R is the organic substituent. Alkoxides are strong bases and, whe ...
(R = alkyl, aryl). Reduction of WCl6 gives, sequentially, tungsten(V) chloride and tungsten(IV) chloride.


Safety considerations

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


References

{{Chlorides Tungsten halides Chlorides Octahedral compounds