Vanadyl Chloride
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Vanadium oxytrichloride is the
inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...
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 ...
VOCl3. This yellow distillable liquid hydrolyzes readily in air. It is an
oxidizing agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or "Electron acceptor, accepts"/"receives" an electron from a (called the , , or ). In ot ...
. It is used as a
reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
in
organic synthesis Organic synthesis is a special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one o ...
. Samples often appear red or orange owing to an impurity of
vanadium tetrachloride Vanadium tetrachloride is the inorganic compound with the formula V Cl4. This bright red liquid serves as a useful reagent for the preparation of other vanadium compounds. Synthesis, bonding, basic properties With one more valence electron than ...
.


Properties

VOCl3 is a vanadium compound with vanadium in the +5 oxidation state and as such is
diamagnetic Diamagnetic materials are repelled by a magnetic field; an applied magnetic field creates an induced magnetic field in them in the opposite direction, causing a repulsive force. In contrast, paramagnetic and ferromagnetic materials are attracted ...
. It is
tetrahedral In geometry, a tetrahedron (plural: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular faces, six straight edges, and four vertex corners. The tetrahedron is the simplest of all the o ...
with O-V-Cl bond angles of 111° and Cl-V-Cl bond angles of 108°. The V-O and V-Cl bond lengths are 157 and 214 pm, respectively. VOCl3 is highly reactive toward water and evolves
HCl HCL may refer to: Science and medicine * Hairy cell leukemia, an uncommon and slowly progressing B cell leukemia * Harvard Cyclotron Laboratory, from 1961 to 2002, a proton accelerator used for research and development * Hollow-cathode lamp, a spe ...
upon standing. It is soluble in nonpolar solvents such as
benzene Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...
, CH2Cl2, and
hexane Hexane () is an organic compound, a straight-chain alkane with six carbon atoms and has the molecular formula C6H14. It is a colorless liquid, odorless when pure, and with boiling points approximately . It is widely used as a cheap, relatively ...
. In some aspects, the chemical properties of VOCl3 and POCl3 are similar. One distinction is that VOCl3 is a strong oxidizing agent, whereas the phosphorus compound is not. Neat VOCl3 is the usual chemical shift standard for 51V NMR spectroscopy.


Preparation

VOCl3 arises by the
chlorination Chlorination may refer to: * Chlorination reaction In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transform ...
of V2O5. The reaction proceeds near 600 °C: :3 Cl2 + V2O5 → 2 VOCl3 + 1.5 O2 Heating an intimate (well-blended with tiny particles) mixture of V2O5, chlorine, and
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
at 200–400 °C also gives VOCl3. In this case the carbon serves as a
deoxygenation Deoxygenation is a chemical reaction involving the removal of oxygen atoms from a molecule. The term also refers to the removal of molecular oxygen (O2) from gases and solvents, a step in air-free technique and gas purifiers. As applied to orga ...
agent akin to its use in the
chloride process The chloride process is used to separate titanium from its ores. The goal of the process is to win high purity titanium dioxide from ores such as ilmenite (FeTiO3) and rutile (TiO2). The strategy exploits the volatility of TiCl4, which is readily p ...
for the manufacturing of TiCl4 from TiO2. Vanadium(III) oxide can also be used as a precursor: :3 Cl2 + V2O3 → 2 VOCl3 + 0.5 O2 A more typical laboratory synthesis involves the chlorination of V2O5 using SOCl2. :V2O5 + 3 SOCl2 → 2 VOCl3 + 3 SO2


Reactions


Hydrolysis and alcoholysis

VOCl3 quickly hydrolyzes resulting in
vanadium pentoxide Vanadium(V) oxide (''vanadia'') is the inorganic compound with the formula V2 O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because o ...
and
hydrochloric acid Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid Acid strength is the tendency of an acid, symbol ...
. In the picture, orange V2O5 can be seen forming on the walls of the beaker. An intermediate in this process is VO2Cl: :2 VOCl3 + 3 H2O → V2O5 + 6 HCl VOCl3 reacts with alcohols especially in the presence of a proton-acceptor to give
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 ...
s, as illustrated by this synthesis of
vanadyl isopropoxide Vanadyl isopropoxide is the metal alkoxide with the formula VO(O-iPr)3 (iPr = CH(CH3)2). A yellow volatile liquid, it is a common alkoxide of vanadium. It is used as a reagent and as a precursor to vanadium oxides. The compound is diamagnetic. It ...
: :VOCl3 + 3 HOCH(CH3)2 → VO(OCH(CH3)2)3 + 3 HCl


Interconversions to other V-O-Cl compounds

VOCl3 is also used in the synthesis of
vanadium oxydichloride Vanadium oxydichloride is the inorganic compound with the formula VOCl2. One of several oxychlorides of vanadium, it is a hygroscopic green solid. It is prepared by comproportionation of vanadium trichloride and vanadium(V) oxides: :V2O5 + VO ...
. :V2O5 + 3 VCl3 + VOCl3 → 6 VOCl2 VO2Cl can be prepared by an unusual reaction involving Cl2O. :VOCl3 + Cl2O → VO2Cl + 2 Cl2 At >180 °C, VO2Cl decomposes to V2O5 and VOCl3. Similarly, VOCl2 also decomposes to give VOCl3, together with VOCl.


Adduct formation

VOCl3 is strongly
Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...
ic, as demonstrated by its tendency to form
adduct An adduct (from the Latin ''adductus'', "drawn toward" alternatively, a contraction of "addition product") is a product of a direct addition of two or more distinct molecules, resulting in a single reaction product containing all atoms of all co ...
s with various bases such as
acetonitrile Acetonitrile, often abbreviated MeCN (methyl cyanide), is the chemical compound with the formula and structure . This colourless liquid is the simplest organic nitrile (hydrogen cyanide is a simpler nitrile, but the cyanide anion is not clas ...
and
amine In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituen ...
s. In forming the adducts, vanadium changes from four-coordinate tetrahedral geometry to six-coordinate octahedral geometry: :VOCl3 + 2 H2NEt → VOCl3(H2NEt)2


VOCl3 in alkene polymerization

VOCl3 is used as a catalyst or precatalyst in production of ethylene-propylene rubbers (EPDM).


References

{{Vanadium compounds Vanadium(V) compounds Oxychlorides Metal halides Vanadyl compounds