Vanadium tetrachloride

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Vanadium tetrachloride
Structural formula of the vanadium tetrachloride molecule Vanadium tetrachloride.svg
Structural formula of the vanadium tetrachloride molecule
3D model of the vanadium tetrachloride molecule Vanadium-tetrachloride-3D-balls.png
3D model of the vanadium tetrachloride molecule
IUPAC names
Vanadium tetrachloride
Vanadium(IV) chloride
3D model (JSmol)
ECHA InfoCard 100.028.692 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 231-561-1
PubChem CID
RTECS number
  • YW2625000
  • InChI=1S/4ClH.2V/h4*1H;;/q;;;;2*+2/p-4 Yes check.svgY
  • InChI=1/4ClH.2V/h4*1H;;/q;;;;2*+2/p-4
  • Cl[V](Cl)(Cl)Cl
Molar mass 192.75 g/mol
Appearancebright red liquid, moisture sensitive
Odor pungent
Density 1.816 g/cm3, liquid
Melting point −24.5 °C (−12.1 °F; 248.7 K)
Boiling point 148 °C (298 °F; 421 K)
Solubility soluble in CH2Cl2
Vapor pressure 7.9 Pa
+1130.0·10−6 cm3/mol
0 D
Occupational safety and health (OHS/OSH):
Main hazards
toxic; oxidizer; hydrolyzes to release HCl
NFPA 704 (fire diamond)
Lethal dose or concentration (LD, LC):
160 mg/kg (rat, oral)
Related compounds
Other anions
vanadium tetrafluoride, vanadium disulfide, vanadium tetrabromide
Other cations
titanium tetrachloride, chromium tetrachloride, niobium tetrachloride, tantalum tetrachloride
Related compounds
vanadium trichloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Vanadium tetrachloride is the inorganic compound with the formula V Cl 4. This reddish-brown liquid serves as a useful reagent for the preparation of other vanadium compounds.


Synthesis, bonding, basic properties

With one more valence electron than diamagnetic TiCl4, VCl4 is a paramagnetic liquid. It is one of only a few paramagnetic compounds that is liquid at room temperature.

VCl4 is prepared by chlorination of vanadium metal. VCl5 does not form in this reaction; Cl2 lacks the oxidizing power to attack VCl4. VCl5 can however be prepared indirectly from VF5 at −78 °C. [1]


Consistent with its high oxidizing power, VCl4 reacts with HBr at -50 °C to produce VBr3. The reaction proceeds via VBr4, which releases Br2 during warming to room temperature. [2]

2 VCl4 + 8 HBr → 2 VBr3 + 8 HCl + Br2

VCl4 forms adducts with many donor ligands, for example, VCl4(THF)2.

It is the precursor to vanadocene dichloride.

Organic chemistry

In organic synthesis, VCl4 is used for the oxidative coupling of phenols. For example, it converts phenol into a mixture of 4,4'-, 2,4'-, and 2,2'-biphenols: [3]

2 C6H5OH + 2 VCl4 → HOC6H4–C6H4OH + 2 VCl3 + 2 HCl


VCl4 is a catalyst for the polymerization of alkenes, especially those useful in the rubber industry. The underlying technology is related to Ziegler–Natta catalysis, which involves the intermediacy of vanadium alkyls.

Safety considerations

VCl4 is a volatile, aggressive oxidant that readily hydrolyzes to release HCl.

Related Research Articles

<span class="mw-page-title-main">Haloalkane</span> Group of chemical compounds derived from alkanes containing one or more halogens

The haloalkanes are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes that contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

In organic chemistry, an acyl chloride is an organic compound with the functional group −C(=O)Cl. Their formula is usually written R−COCl, where R is a side chain. They are reactive derivatives of carboxylic acids. A specific example of an acyl chloride is acetyl chloride, CH3COCl. Acyl chlorides are the most important subset of acyl halides.

In organic chemistry, an aryl halide is an aromatic compound in which one or more hydrogen atoms, directly bonded to an aromatic ring are replaced by a halide. The haloarene are different from haloalkanes because they exhibit many differences in methods of preparation and properties. The most important members are the aryl chlorides, but the class of compounds is so broad that there are many derivatives and applications.

<span class="mw-page-title-main">Titanium tetrachloride</span> Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as "tickle" or "tickle 4" due to the phonetic resemblance of its molecular formula to the word.

Cuprate loosely refers to a material that can be viewed as containing anionic copper complexes. Examples include tetrachloridocuprate ([CuCl4]2−), the superconductor YBa2Cu3O7, and the organocuprates (e.g., dimethylcuprate [Cu(CH3)2]). The term cuprates derives from the Latin word for copper, cuprum. The term is mainly used in three contexts: oxide materials, anionic coordination complexes, and anionic organocopper compounds.

<span class="mw-page-title-main">Hydrogen bromide</span> Chemical compound

Hydrogen bromide is the inorganic compound with the formula HBr. It is a hydrogen halide consisting of hydrogen and bromine. A colorless gas, it dissolves in water, forming hydrobromic acid, which is saturated at 68.85% HBr by weight at room temperature. Aqueous solutions that are 47.6% HBr by mass form a constant-boiling azeotrope mixture that boils at 124.3 °C. Boiling less concentrated solutions releases H2O until the constant-boiling mixture composition is reached.

<span class="mw-page-title-main">Aluminium chloride</span> Chemical compound

Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula AlCl3. It forms hexahydrate with the formula [Al(H2O)6]Cl3, containing six water molecules of hydration. Both are colourless crystals, but samples are often contaminated with iron(III) chloride, giving a yellow color.

<span class="mw-page-title-main">Copper(II) chloride</span> Chemical compound

Copper(II) chloride is the chemical compound with the chemical formula CuCl2. The anhydrous form is yellowish brown but slowly absorbs moisture to form a blue-green dihydrate.

<span class="mw-page-title-main">Sulfonic acid</span> Organic compounds with the structure R−S(=O)2−OH

In organic chemistry, sulfonic acid refers to a member of the class of organosulfur compounds with the general formula R−S(=O)2−OH, where R is an organic alkyl or aryl group and the S(=O)2(OH) group a sulfonyl hydroxide. As a substituent, it is known as a sulfo group. A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group replaced by an organic substituent. The parent compound is the parent sulfonic acid, HS(=O)2(OH), a tautomer of sulfurous acid, S(=O)(OH)2. Salts or esters of sulfonic acids are called sulfonates.

<span class="mw-page-title-main">Triphenylphosphine</span> Chemical compound

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

<span class="mw-page-title-main">Diazonium compound</span> Diazonium salts of formula R-N≡N+

Diazonium compounds or diazonium salts are a group of organic compounds sharing a common functional group [R−N+≡N]X where R can be any organic group, such as an alkyl or an aryl, and X is an inorganic or organic anion, such as a halide.

<span class="mw-page-title-main">Vanadium oxytrichloride</span> Chemical compound

Vanadium oxytrichloride is the inorganic compound with the formula VOCl3. This yellow distillable liquid hydrolyzes readily in air. It is an oxidizing agent. It is used as a reagent in organic synthesis. Samples often appear red or orange owing to an impurity of vanadium tetrachloride.

<span class="mw-page-title-main">Vanadium(III) chloride</span> Chemical compound

Vanadium trichloride is the inorganic compound with the formula VCl3. This purple salt is a common precursor to other vanadium(III) complexes.

<span class="mw-page-title-main">Molybdenum(V) chloride</span> Chemical compound

Molybdenum(V) chloride is the inorganic compound with the empirical formula MoCl5. This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents.

<span class="mw-page-title-main">Vanadium(III) bromide</span> Chemical compound

Vanadium(III) bromide, also known as vanadium tribromide, is the inorganic compound with the formula VBr3. It is a green-black solid. In terms of its structure, the compound is polymeric with octahedral vanadium(III) surrounded by six bromide ligands.

<span class="mw-page-title-main">Vanadium(II) chloride</span> Chemical compound

Vanadium(II) chloride is the inorganic compound with the formula VCl2, and is the most reduced vanadium chloride. Vanadium(II) chloride is an apple-green solid that dissolves in water to give purple solutions.

Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.

<span class="mw-page-title-main">4,4'-Biphenol</span> Chemical compound

4,4′-Biphenol is an organic compound which is a phenolic derivative of biphenyl. It is a colorless solid.

<span class="mw-page-title-main">Organobismuth chemistry</span>

Organobismuth chemistry is the chemistry of organometallic compounds containing a carbon to bismuth chemical bond. Applications are few. The main bismuth oxidation states are Bi(III) and Bi(V) as in all higher group 15 elements. The energy of a bond to carbon in this group decreases in the order P > As > Sb > Bi. The first reported use of bismuth in organic chemistry was in oxidation of alcohols by Challenger in 1934 (using Ph3Bi(OH)2). Knowledge about methylated species of bismuth in environmental and biological media is limited.

Organovanadium chemistry is the chemistry of organometallic compounds containing a carbon (C) to vanadium (V) chemical bond. Organovanadium compounds find only minor use as reagents in organic synthesis but are significant for polymer chemistry as catalysts.


  1. Tamadon, Farhad; Seppelt, Konrad (2013). "The Elusive Halides VCl5, MoCl6, and ReCl6". Angew. Chem. Int. Ed. 52 (2): 767–769. doi:10.1002/anie.201207552. PMID   23172658.
  2. Calderazzo, F.; Maichle-Mössmer, C.; G., Pampaloni; J., Strähle (1993). "Low-temperature Syntheses of Vanadium(III) and Molybdenum(IV) Bromides by Halide Exchange". Dalton Transactions (5): 655–8. doi:10.1039/DT9930000655.
  3. O’Brien, M. K.; Vanasse, B. (2001). "Vanadium(IV) Chloride". In Paquette, L. (ed.). Encyclopedia of Reagents for Organic Synthesis. New York, NY: J. Wiley & Sons. doi:10.1002/047084289X.rv001. ISBN   0471936235.