Vanadium tetrachloride

Vanadium tetrachloride
Structural formula of the vanadium tetrachloride molecule	3D model of the vanadium tetrachloride molecule
Names
	IUPAC names Vanadium tetrachloride; Vanadium(IV) chloride
Identifiers
CAS Number	7632-51-1 ;
3D model (JSmol)	Interactive image;
ChemSpider	19956660 ;
ECHA InfoCard	100.028.692
EC Number	231-561-1;
PubChem CID	24273;
RTECS number	YW2625000;
UNII	2I17MGM5YJ ;
CompTox Dashboard (EPA)	DTXSID0064757 ;
	InChI InChI=1S/4ClH.2V/h41H;;/q;;;;2+2/p-4 Key: UNUHYFVFMNJHJW-UHFFFAOYSA-J ; InChI=1/4ClH.2V/h41H;;/q;;;;2+2/p-4 Key: UNUHYFVFMNJHJW-XBHQNQODAR;
	SMILES Cl[V](Cl)(Cl)Cl;
Properties
Chemical formula	VCl4
Molar mass	192.75 g/mol
Appearance	bright 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 in water	decomposes
Solubility	soluble in CH2Cl2
Vapor pressure	7.9 Pa
Magnetic susceptibility (χ)	+1130.0·10−6 cm3/mol
Structure
Coordination geometry	tetrahedral
Dipole moment	0 D
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	toxic; oxidizer; hydrolyzes to release HCl
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H301, H311, H314, H331
Precautionary statements	P260, P262, P264, P270, P271, P280, P301+P316, P301+P330+P331, P302+P352, P302+P361+P354, P304+P340, P305+P354+P338, P316, P321, P330, P361+P364, P363, P403+P233, P405, P501
NFPA 704 (fire diamond)	3 0 2 W
	Lethal dose or concentration (LD, LC):
LD50 (median dose)	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). verify (what is ?) Infobox references

Vanadium tetrachloride is the inorganic compound with the formula V Cl₄. 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.^[2]

Reactions

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.^[3]

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:^[4]

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

Applications

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.

References

↑ PubChem. "Vanadium tetrachloride". pubchem.ncbi.nlm.nih.gov. Retrieved 2026-02-04.
↑ 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.
↑ 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.
↑ 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.

[1] PubChem. "Vanadium tetrachloride". pubchem.ncbi.nlm.nih.gov. Retrieved 2026-02-04.

[2] 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.

[3] 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.

[4] 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.

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