Vanadium(III) chloride

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Vanadium(III) chloride
Plan view of a single layer in the crystal structure of vanadium(III) chloride VCl3-layer-in-xtal-1947-3D-balls.png
Plan view of a single layer in the crystal structure of vanadium(III) chloride
Layer stacking in the crystal structure of vanadium(III) chloride VCl3-xtal-1947-3D-balls.png
Layer stacking in the crystal structure of vanadium(III) chloride
Names
IUPAC names
Vanadium(III) chloride
Vanadium trichloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.028.859 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
RTECS number
  • YW2800000
  • InChI=1S/3ClH.V/h3*1H;/q;;;+3/p-3 Yes check.svgY
    Key: HQYCOEXWFMFWLR-UHFFFAOYSA-K Yes check.svgY
  • InChI=1/3ClH.V/h3*1H;/q;;;+3/p-3
    Key: HQYCOEXWFMFWLR-DFZHHIFOAB
  • [V+3].[Cl-].[Cl-].[Cl-]
Properties
VCl3
Molar mass 157.30 g/mol
Appearanceviolet crystals
paramagnetic
Density 3.0 g/cm3 (20 °C)
Melting point > 300 °C (572 °F; 573 K)(decomposes)
soluble
+3030.0·10−6 cm3/mol
Structure
Trigonal, hR24
R-3, No. 148
Hazards
Safety data sheet Vanadium(III) Chloride
GHS classification and labelling: [1]
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg
Danger
H302, H314
P280, P305, P310, P338, P351
Flash point Non-flammable
Related compounds
Other anions
vanadium trifluoride, vanadium tribromide
Other cations
titanium trichloride, chromium(III) chloride, niobium trichloride, tantalum trichloride
Related compounds
 vanadium dichloride, vanadium tetrachloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Vanadium trichloride is the inorganic compound with the formula VCl3. This purple salt is a common precursor to other vanadium(III) complexes. [2]

Contents

Structure

VCl3 has the common BiI3 structure, a motif that features hexagonally closest-packed chloride framework with vanadium ions occupying the octahedral holes. VBr3 and VI3 adopt the same structure, but VF3 features a structure more closely related to ReO3. VCl3 is paramagnetic and has two unpaired electrons.

Preparation and reactions

VCl3 is prepared by heating VCl4 at 160–170 °C under a flowing stream of inert gas, which sweeps out the Cl2. The bright red liquid converts to a purple solid.

Heating of VCl3 decomposes with volatilization of VCl4, leaving VCl2. [3] Upon heating under H2 at 675 °C (but less than 700 °C), VCl3 reduces to greenish VCl2.

2 VCl3 + H2 → 2 VCl2 + 2 HCl

Comproportionation of vanadium trichloride and vanadium(V) oxides gives vanadium oxydichloride: [4]

V2O5 + VOCl3 + 3 VCl3 → 6 VOCl2

Vanadium trichloride catalyses the pinacol coupling reaction of benzaldehyde (PhCHO) to 1,2-diphenyl-1,2-ethanediol by various reducing metals such as zinc: [5]

Zn + 2 H2O + 2 PhCHO → (PhCH(OH))2 + Zn(OH)2

Complexes

VCl3 forms colorful adducts and derivatives with a broad scale of ligands. VCl3 dissolves in water to give the hexahydrate, but the formula is deceptive. The salt is described by the formula [VCl2(H2O)4]Cl.2H2O. In other words, two of the water molecules are not bound to the vanadium, whose structure resembles the corresponding Fe(III) derivative. Removal of the two bound chloride ligands from [VCl2(H2O)4]+ in aqueous solution gives the green ion [V(H2O)6]3+. [6]

Structure of VCl3(thf)3. CSD CIF CANZOG10.png
Structure of VCl3(thf)3.

With tetrahydrofuran, VCl3 forms the red/pink complex VCl3(THF)3. [8] Vanadium(III) chloride reacts with acetonitrile to give the green adduct VCl3(MeCN)3. When treated with KCN, VCl3 converts to [V(CN)7]4− (early metals commonly adopt coordination numbers greater than 6 with compact ligands). Complementarily, larger metals can form complexes with rather bulky ligands. This aspect is illustrated by the isolation of VCl3(NMe3)2, containing two bulky NMe3 ligands.

Organometallic derivatives

Vanadium(III) chloride as its thf complex is a precursor toV(mesityl)3. [9]

VCl3(THF)3 + 3 LiC6H2-2,4,6-Me3 → V(C6H2-2,4,6-Me3)3(THF) + 3 LiCl

Related Research Articles

Titanium tetrachloride 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 spectacular opaque clouds of titanium dioxide (TiO2) and hydrated hydrogen chloride. It is sometimes referred to as "tickle" or "tickle 4" due to the phonetic resemblance of its molecular formula (TiCl4) to the word.

Aluminium chloride Chemical compound

Aluminium chloride (AlCl3), also known as aluminium trichloride, describe compounds with the formula AlCl3(H2O)n (n = 0 or 6). They consist of aluminium and chlorine atoms in a 1:3 ratio, and one form also contains six waters of hydration. Both are white solids, but samples are often contaminated with iron(III) chloride, giving a yellow color.

Manganese(II) chloride Chemical compound

Manganese(II) chloride is the dichloride salt of manganese, MnCl2. This inorganic chemical exists in the anhydrous form, as well as the dihydrate (MnCl2·2H2O) and tetrahydrate (MnCl2·4H2O), with the tetrahydrate being the most common form. Like many Mn(II) species, these salts are pink, with the paleness of the color being characteristic of transition metal complexes with high spin d5 configurations. It is a paramagnetic salt.

Chromium(III) chloride Chemical compound

Chromium(III) chloride (also called chromic chloride) describes any of several compounds of with the formula CrCl3 · xH2O, where x can be 0, 5, and 6. The anhydrous compound with the formula CrCl3 is a violet solid. The most common form of the trichloride is the dark green hexahydrate, CrCl3 · 6 H2O. Chromium chlorides find use as catalysts and as precursors to dyes for wool.

Phosphorus trichloride Chemical compound

Phosphorus trichloride is a inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts violently with water to release hydrogen chloride.

Scandium chloride Chemical compound

Scandium(III) chloride is the inorganic compound with the formula ScCl3. It is a white, high-melting ionic compound, which is deliquescent and highly water-soluble. This salt is mainly of interest in the research laboratory. Both the anhydrous form and hexahydrate (ScCl3•6H2O) are commercially available.

Hafnium tetrachloride Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

Vanadium oxytrichloride 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.

Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins.

Vanadium tetrachloride is the inorganic compound with the formula VCl4. This bright red liquid serves as a useful reagent for the preparation of other vanadium compounds.

Molybdenum(V) chloride Chemical compound

Molybdenum(V) chloride is the inorganic compound with the formula [MoCl5]2. This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents. Usually called molybdenum pentachloride, it is in fact a dimer with the formula Mo2Cl10.

Vanadium(II) chloride 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.

Molybdenum tetrachloride Chemical compound

Molybdenum tetrachloride is the inorganic compound with the empirical formula MoCl4. The material exists as two polymorphs, a polymeric ("α") and a hexameric ("β") structure. In each polymorph, the Mo center is octahedral with two terminal chloride ligands and four doubly bridging ligands.

Niobium(IV) chloride Chemical compound

Niobium(IV) chloride, also known as niobium tetrachloride, is the chemical compound of formula NbCl4. This compound exists as dark violet crystals, is highly sensitive to air and moisture, and disproportiates into niobium(III) chloride and niobium(V) chloride when heated.

Organovanadium chemistry is the chemistry of organometallic compounds containing a carbon 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 bis(trimethylsilyl)amides

Metal bis(trimethylsilyl)amides are coordination complexes composed of a cationic metal with anionic bis(trimethylsilyl)amide ligands and are part of a broader category of metal amides.

Vanadium oxydichloride 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:

Niobium(III) chloride also known as niobium trichloride is a compound of niobium and chlorine. The binary phase NbCl3 is not well characterized but many adducts are known.

Tantalum(III) chloride Chemical compound

Tantalum(III) chloride or tantalum trichloride is non-stoichiometric with a range of composition from TaCl2.9 to TaCl3.1 Anionic and neutral clusters containing Ta(III) chloride include [Ta6Cl18]4− and [Ta6Cl14](H2O)4.

Transition metal chloride complex Coordination complex

In chemistry, a transition metal chloride complex is a coordination complex that consists of a transition metal coordinated to one or more chloride ligand. The class of complexes is extensive.

References

  1. ↑ "Vanadium(III) Chloride SDS". American Elements . Retrieved 2018-08-17.
  2. ↑ Holleman, A. F.; Wiberg, E. Inorganic Chemistry Academic Press: San Diego, 2001. ISBN   0-12-352651-5.
  3. ↑ Young, Ralph C.; Smith, Maynard E.; Moeller, Therald; Gordon, Paul G.; McCullough, Fred (2007). "Vanadium(III) Chloride". Inorganic Syntheses. pp. 128–130. doi:10.1002/9780470132357.ch43. ISBN   9780470132357.
  4. ↑ G. Brauer (1963). "Vanadium Oxydichloride". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. NY: Academic Press. p. 1263.
  5. ↑ Xu; Hirao, Toshikazu (2005). "Vanadium-Catalyzed Pinacol Coupling Reaction in Water". The Journal of Organic Chemistry. 70 (21): 8594–8596. doi:10.1021/jo051213f. PMID   16209617.
  6. ↑ Donovan, William F.; Smith, Peter W. (1975). "Crystal and Molecular Structures of Aquahalogenovanadium(III) Complexes. Part I. X-Ray Crystal Structure of trans-Tetrakisaquadibromo-Vanadium(III) Bromide Dihydrate and the Isomorphous Chloro- Compound". Journal of the Chemical Society, Dalton Transactions (10): 894. doi:10.1039/DT9750000894.
  7. ↑ Albert Cotton, F.; Duraj, Stan A.; Powell, Gregory L.; Roth, Wieslaw J. (1986). "Comparative Structural Studies of the First Row Early Transition Metal(III) Chloride Tetrahydrofuran Solvates". Inorganica Chimica Acta. 113: 81. doi:10.1016/S0020-1693(00)86863-2.
  8. ↑ Manzer, L. E. (1982). Tetrahydrofuran Complexes of Selected Early Transition Metals. Inorganic Syntheses. 21. pp. 135–140. doi:10.1002/9780470132524.ch31.
  9. ↑ Vivanco, Marilin; Ruiz, Javier; Floriani, Carlo; Chiesi-Villa, Angiola; Rizzoli, Corrado (1993). "Chemistry of the vanadium-carbon .sigma. Bond. 2. Oxovanadium(IV) and oxovanadium(V) containing metal-to-carbon .sigma. Bonds". Organometallics. 12 (5): 1802–1810. doi:10.1021/om00029a042.
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