Vanadium tetrachloride

Chemical reagent used to produce other vanadium compounds

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 Y

3D model (JSmol)

* Interactive image

ChemSpider |

* 19956660 Y

ECHA InfoCard | 100.028.692
EC Number |

* 231-561-1

PubChem CID

* 24273

RTECS number |

* YW2625000

UNII |

* 2I17MGM5YJ Y

CompTox Dashboard (EPA)

* DTXSID0064757

InChI

* InChI=1S/4ClH.2V/h4*1H;;/q;;;;2*+2/p-4 Y

Key: UNUHYFVFMNJHJW-UHFFFAOYSA-J Y

* InChI=1/4ClH.2V/h4*1H;;/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
NFPA 704 (fire diamond)  |

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).

Y verify (what is YN ?)

Infobox references

Chemical compound

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

## Synthesis, bonding, basic properties

[edit]

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]

## Reactions

[edit]

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

[edit]

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

## Applications

[edit]

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

[edit]

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

## References

[edit]

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.

* v
* t
* e

Vanadium compounds

Vanadium(0)|

* V(CO)6

Vanadium(II)|

* VF2
* VBr2
* VCl2
* VI2
* VO
* VS
* VSO4

Vanadium(III)|

* VBr3
* VCl3
* VF3
* VI3
* VN
* V2O3
* V2(SO4)3
* V2S3

| Organovanadium(III) compounds|

* V(C9H11)3

|

Vanadium(IV)|

* VC
* VO2
* VOCl2
* V(S2)2
* VCl4
* VF4

| Organovanadium(IV) compounds|

* VO(C5H7O2)2

|

Vanadyl(IV) compounds|

* VOSO4
* VO(CH3COO)2

Oxovanadates(IV)|

* Lu2V2O7

Vanadium(V)|

* V2O5
* VO2F
* VF5
* VCl5
* VCl3NCl
* VO+

| Vanadyl(V) compounds|

* VOPO4
* VO(ClO4)3
* VOCl3
* VOF3
* VO(NO3)3

|

Oxovanadates(V)|

* BiVO4
* NH3VO3
* NaVO3
* Na3VO4
* Na6V10O28
* NdVO3
* YVO3

* v
* t
* e

Salts and covalent derivatives of the chloride ion

| HCl |  |  |  | He

|
|
|
|

LiCl | BeCl2 | B4Cl4
B12Cl12
BCl3
B2Cl4
+BO3 | C2Cl2
C2Cl4
C2Cl6
CCl4

+CO3 | NCl3
ClN3

+NO3 | ClxOy
Cl2O
Cl2O2
ClO
ClO2
Cl2O4
Cl2O6
Cl2O7
ClO4
+O | ClF
ClF3
ClF5 | Ne
NaCl | MgCl2 | AlCl
AlCl3 | Si5Cl12
Si2Cl6
SiCl4 | P2Cl4
PCl3
PCl5
+P | S2Cl2
SCl2
SCl4
+SO4 | Cl2 | Ar
KCl | CaCl
CaCl2 |  | ScCl3 | TiCl2
TiCl3
TiCl4 | VCl2
VCl3
VCl4
VCl5 | CrCl2
CrCl3
CrCl4 | MnCl2
MnCl3 | FeCl2
FeCl3 | CoCl2
CoCl3 | NiCl2 | CuCl
CuCl2 | ZnCl2 | GaCl
GaCl3 | GeCl2
GeCl4 | AsCl3
AsCl5
+As | Se2Cl2
SeCl2
SeCl4 | BrCl | Kr
RbCl | SrCl2 |  | YCl3 | ZrCl2
ZrCl3
ZrCl4 | NbCl3
NbCl4
NbCl5 | MoCl2
MoCl3
MoCl4
MoCl5
MoCl6 | TcCl3
TcCl4 | RuCl2
RuCl3
RuCl4 | RhCl3 | PdCl2 | AgCl | CdCl2 | InCl
InCl2
InCl3 | SnCl2
SnCl4 | SbCl3
SbCl5 | Te3Cl2
TeCl2
TeCl4 | ICl
ICl3 | XeCl
XeCl2
XeCl4
CsCl | BaCl2 | *  | LuCl3 | HfCl4 | TaCl3
TaCl4
TaCl5 | WCl2
WCl3
WCl4
WCl5
WCl6 | ReCl3
ReCl4
ReCl5
ReCl6 | OsCl2
OsCl3
OsCl4
OsCl5 | IrCl2
IrCl3
IrCl4 | PtCl2
PtCl4 | AuCl
(Au[AuCl4])2
AuCl3 | Hg2Cl2
HgCl2 | TlCl
TlCl3 | PbCl2
PbCl4 | BiCl3 | PoCl2
PoCl4 | AtCl | Rn
FrCl | RaCl2 | **  | LrCl3 | RfCl4 | DbCl5 | SgO2Cl2 | BhO3Cl | Hs  | Mt  | Ds  | Rg  | Cn  | Nh  | Fl  | Mc  | Lv  | Ts  | Og

*  | LaCl3 | CeCl3 | PrCl3 | NdCl2
NdCl3 | PmCl3 | SmCl2
SmCl3 | EuCl2
EuCl3 | GdCl3 | TbCl3 | DyCl2
DyCl3 | HoCl3 | ErCl3 | TmCl2
TmCl3 | YbCl2
YbCl3
**  | AcCl3 | ThCl3
ThCl4 | PaCl4
PaCl5 | UCl3
UCl4
UCl5
UCl6 | NpCl3
NpCl4 | PuCl3 | AmCl2
AmCl3 | CmCl3 | BkCl3 | CfCl3
CfCl2 | EsCl2
EsCl3 | FmCl2 | MdCl2 | NoCl2
*[CID]: Compound ID
*[EPA]: U.S. Environmental Protection Agency
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