Vanadium oxytrichloride

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Vanadium oxytrichloride
Vanadyl-chloride-3D-balls.png
Vanadium oxytrichloride.png
Names
IUPAC name
Vanadium trichloride oxide
Other names
  • Vanadyl chloride
  • Vanadyl trichloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.028.892 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 231-780-2
MeSH trichlorooxo+vanadium
PubChem CID
RTECS number
  • YW2975000
UNII
UN number 2443
  • InChI=1S/3ClH.O.V/h3*1H;;/q;;;;+3/p-3 X mark.svgN
    Key: JBIQAPKSNFTACH-UHFFFAOYSA-K X mark.svgN
  • Cl[V](Cl)(Cl)=O
Properties
VOCl
3
Molar mass 173.300 g mol−1
Appearanceyellow liquid
Density 1.826 g mL−1
Melting point −76.5 °C (−105.7 °F; 196.7 K)
Boiling point 126.7 °C (260.1 °F; 399.8 K)
Decomposes
Vapor pressure 1.84 kPa (at 20 °C)
Structure
Tetrahedral
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-pollu.svg
Danger
H301, H314
P280, P301+P310, P305+P351+P338, P310
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazards (white): no code
3
1
3
Lethal dose or concentration (LD, LC):
140 mg kg−1 (oral, rat)
Related compounds
Related vanadiums
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

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. [1] Samples often appear red or orange owing to an impurity of vanadium tetrachloride. [2]

Contents

Properties

VOCl3 is a vanadium compound with vanadium in the +5 oxidation state and as such is diamagnetic. It is tetrahedral 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 upon standing. It is soluble in nonpolar solvents such as benzene, CH2Cl2, and hexane. 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. [3] Neat VOCl3 is the usual chemical shift standard for 51V NMR spectroscopy. [4]

Preparation

VOCl3 arises by the chlorination of V2O5. The reaction proceeds near 600 °C: [5]

3 Cl2 + V2O5 → 2 VOCl3 + 1.5 O2

Heating an intimate (well-blended with tiny particles) mixture of V2O5, chlorine, and carbon at 200–400 °C also gives VOCl3. In this case the carbon serves as a deoxygenation agent akin to its use in the chloride process for the manufacturing of TiCl4 from TiO2.

Vanadium(III) oxide can also be used as a precursor: [2]

3 Cl2 + V2O3 → 2 VOCl3 + 0.5 O2

A more typical laboratory synthesis involves the chlorination of V2O5 using SOCl2. [6]

V2O5 + 3 SOCl2 → 2 VOCl3 + 3 SO2

Reactions

Hydrolysis and alcoholysis

VOCl3 quickly hydrolyzes resulting in vanadium pentoxide and hydrochloric acid. 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 alkoxides, as illustrated by this synthesis of vanadyl isopropoxide:

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.

V2O5 + 3 VCl3 + VOCl3 → 6 VOCl2

VO2Cl can be prepared by an unusual reaction involving Cl2O. [7]

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 acidic, as demonstrated by its tendency to form adducts with various bases such as acetonitrile and amines. In forming the adducts, vanadium changes from four-coordinate tetrahedral geometry to six-coordinate octahedral geometry:

VOCl3 + 2 H2NEt → VOCl3(H2NEt)2

Organic chemistry

VOCl3 is a catalyst or precatalyst in production of ethylene-propylene rubbers (EPDM). In organic synthesis, it has been used for oxidative coupling of phenols and anisoles. [8]

Related Research Articles

Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are some of the most important and commonplace compounds of iron. They are available both in anhydrous and in hydrated forms which are both hygroscopic. They feature iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while all forms are mild oxidizing agent. It is used as a water cleaner and as an etchant for metals.

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 transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens. Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

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

Zinc chloride is the name of inorganic chemical compounds with the formula ZnCl2. It forms hydrates. Zinc chloride, anhydrous and its hydrates are colorless or white crystalline solids, and are highly soluble in water. Five hydrates of zinc chloride are known, as well as four forms of anhydrous zinc chloride. This salt is hygroscopic and even deliquescent. Zinc chloride finds wide application in textile processing, metallurgical fluxes, and chemical synthesis. No mineral with this chemical composition is known aside from the very rare mineral simonkolleite, Zn5(OH)8Cl2·H2O.

<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.

<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">Dichlorine monoxide</span> Chemical compound

Dichlorine monoxide is an inorganic compound with the molecular formula Cl2O. It was first synthesised in 1834 by Antoine Jérôme Balard, who along with Gay-Lussac also determined its composition. In older literature it is often referred to as chlorine monoxide, which can be a source of confusion as that name now refers to the ClO radical.

<span class="mw-page-title-main">Vanadium(V) oxide</span> Precursor to vanadium alloys and industrial catalyst

Vanadium(V) oxide (vanadia) is the inorganic compound with the formula V2O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because of its high oxidation state, it is both an amphoteric oxide and an oxidizing agent. From the industrial perspective, it is the most important compound of vanadium, being the principal precursor to alloys of vanadium and is a widely used industrial catalyst.

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

Sulfuryl chloride is an inorganic compound with the formula SO2Cl2. At room temperature, it is a colorless liquid with a pungent odor. Sulfuryl chloride is not found in nature, as can be inferred from its rapid hydrolysis.

Boron trichloride is the inorganic compound with the formula BCl3. This colorless gas is a reagent in organic synthesis. It is highly reactive toward water.

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

Titanocene dichloride is the organotitanium compound with the formula (η5-C5H5)2TiCl2, commonly abbreviated as Cp2TiCl2. This metallocene is a common reagent in organometallic and organic synthesis. It exists as a bright red solid that slowly hydrolyzes in air. It shows antitumour activity and was the first non-platinum complex to undergo clinical trials as a chemotherapy drug.

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

Vanadium(III) chloride is the inorganic compound with the formula VCl3 which forms the hexahydrate, [VCl2(H2O)4]Cl·2H2O. This hygroscopic purple salt is a common precursor to other vanadium(III) complexes.

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

Arsenic trichloride is an inorganic compound with the formula AsCl3, also known as arsenous chloride or butter of arsenic. This poisonous oil is colourless, although impure samples may appear yellow. It is an intermediate in the manufacture of organoarsenic compounds.

<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.

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

Vanadium(V) oxytrifluoride is a chemical compound with the formula VOF3. It is one of several vanadium(V) oxyhalides. VOF3 is a yellowish orange powder that is sensitive to moisture. Characteristic of early metal fluorides, the structure is polymeric in the solid state. The solid adopts a layered structure but upon evaporation, the species becomes dimeric. In contrast VOCl3 and VOBr3 remain tetrahedral in all states, being volatile liquids at room temperature.

<span class="mw-page-title-main">Vanadium compounds</span>

Vanadium compounds are compounds formed by the element vanadium (V). The chemistry of vanadium is noteworthy for the accessibility of the four adjacent oxidation states 2–5, whereas the chemistry of the other group 5 elements, niobium and tantalum, are somewhat more limited to the +5 oxidation state. In aqueous solution, vanadium forms metal aquo complexes of which the colours are lilac [V(H2O)6]2+, green [V(H2O)6]3+, blue [VO(H2O)5]2+, yellow-orange oxides [VO(H2O)5]3+, the formula for which depends on pH. Vanadium(II) compounds are reducing agents, and vanadium(V) compounds are oxidizing agents. Vanadium(IV) compounds often exist as vanadyl derivatives, which contain the VO2+ center.

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.

Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion (CH
3
COCHCOCH
3
) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
5
H
7
O
2
in some cases also binds to metals through the central carbon atom; this bonding mode is more common for the third-row transition metals such as platinum(II) and iridium(III).

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

Vanadyl perchlorate or vanadyl triperchlorate is a golden yellow coloured liquid or crystalline compound of vanadium, oxygen and perchlorate group. The substance consists of molecules covalently bound and is quite volatile; it ignites organic solvents on contact and explodes at temperatures above 80 °C.

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

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:

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

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 is prepared by alcoholysis of vanadyl trichloride:

References

  1. O'Brien, Michael K.; Vanasse, Benoit (2001). "Vanadyl Trichloride". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rv004. ISBN   0-471-93623-5.
  2. 1 2 F. E. Brown; F. A. Griffitts (1939). "Hypovanadous Oxide and Vanadium Oxytrichloride". Inorganic Syntheses. pp. 106–108. doi:10.1002/9780470132326.ch38. ISBN   978-0-470-13232-6.{{cite book}}: |journal= ignored (help)
  3. A. Earnshaw, N. Greenwood (1997). The Chemistry of the Elements - Second Edition. pp. 513–514.
  4. Rehder, D.; Polenova, T.; Bühl, M. (2007). Vanadium-51 NMR. Annual Reports on NMR Spectroscopy. Vol. 62. pp. 49–114. doi:10.1016/S0066-4103(07)62002-X. ISBN   978-0-12-373919-3.
  5. Holleman, Arnold Frederik; Wiberg, Egon; Wiberg, Nils (2001). Inorganic Chemistry. Academic Press. ISBN   978-0-12-352651-9.
  6. G. Brauer "Vanadium oxytrichloride" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1264.
  7. Oppermann, H. (1967). "Untersuchungen an Vanadinoxidchloriden und Vanadinchloriden. I. Gleichgewichte mit VOCl3, VO2Cl und VOCl2". Zeitschrift für anorganische und allgemeine Chemie. 351 (3–4): 113–126. doi:10.1002/zaac.19673510302.
  8. O'Brien, Michael K.; Vanasse, Benoit (2001). "Vanadyl Trichloride". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rv004. ISBN   0-471-93623-5.