Vanadium hexacarbonyl

Names
IUPAC name

hexacarbonylvanadium(0)

Identifiers

CAS Number

* 20644-87-5 Y

3D model (JSmol)

* Interactive image

ChEBI |

* CHEBI:37857 Y

ChemSpider |

* 453410

EC Number |

* 243-937-2

Gmelin Reference

| 3893

PubChem CID

* 6097005

UNII |

* WA8Q7FLK2X Y

InChI

* InChI=1S/6CO.V/c6*1-2;

Key: BVSRFQDQORQURQ-UHFFFAOYSA-N

SMILES

* O=C=[V](=C=O)(=C=O)(=C=O)(=C=O)=C=O

Properties

Chemical formula

| C6O6V
Molar mass | 219.00 g/mol
Appearance  | blue-green crystals
yellow solutions
Density | 1.7 g/cm3
Melting point | decomposes
Boiling point | sublimes at 50 °C (122 °F; 323 K) (15 mmHg)

Solubility in water

| insoluble
Solubility in other solvents  | 5 g/L hexane;
more soluble in dichloromethane
Structure

Crystal structure

| orthorhombic

Coordination geometry

| octahedral

Dipole moment

| 0 D
Hazards
Main hazards | CO source
GHS pictograms |
GHS Signal word | Danger

GHS hazard statements

| HH301Script error: No such module "Preview warning".Category:GHS errors, HH330Script error: No such module "Preview warning".Category:GHS errors

GHS precautionary statements

| PP260Script error: No such module "Preview warning".Category:GHS errors, PP264Script error: No such module "Preview warning".Category:GHS errors, PP270Script error: No such module "Preview warning".Category:GHS errors, PP271Script error: No such module "Preview warning".Category:GHS errors, PP284Script error: No such module "Preview warning".Category:GHS errors, PP301+P316Script error: No such module "Preview warning".Category:GHS errors, PP304+P340Script error: No such module "Preview warning".Category:GHS errors, PP316Script error: No such module "Preview warning".Category:GHS errors, PP320Script error: No such module "Preview warning".Category:GHS errors, PP321Script error: No such module "Preview warning".Category:GHS errors, PP330Script error: No such module "Preview warning".Category:GHS errors, PP403+P233Script error: No such module "Preview warning".Category:GHS errors, PP405Script error: No such module "Preview warning".Category:GHS errors, PP501Script error: No such module "Preview warning".Category:GHS errors
Related compounds

Related compounds

* Chromium hexacarbonyl
* Molybdenum hexacarbonyl
* Tungsten hexacarbonyl
* Seaborgium hexacarbonyl
* Dimanganese decacarbonyl
* Dirhenium decacarbonyl
* Iron pentacarbonyl
* Diiron nonacarbonyl
* Triruthenium dodecacarbonyl
* Triosmium dodecacarbonyl
* Dicobalt octacarbonyl
* Tetrarhodium dodecacarbonyl
* Tetrairidium dodecacarbonyl
* Nickel tetracarbonyl

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

Vanadium hexacarbonyl is the inorganic compound with the formula V(CO)6. It is a blue-black volatile solid. This highly reactive species is noteworthy from theoretical perspectives as a rare isolable homoleptic metal carbonyl that is paramagnetic. Most species with the formula Mx(CO)y follow the 18-electron rule, whereas V(CO)6 has 17 valence electrons.[2]

## Contents

* 1 Structure
* 2 Synthesis
* 3 Reactions
* 4 References
* 5 Further reading

## Structure

V(CO)6 adopts an octahedral coordination geometry and is isostructural with chromium hexacarbonyl, even though they have differing valence electron counts. High resolution X-ray crystallography indicates that the molecule is slightly distorted with two (axial) shorter V–C distances of 1.993(2) Å vs. four (equatorial) 2.005(2) Å. Even though V(−I) is a larger ion than V(0), the V–C distances in V(CO)−6 are 0.07 Å shorter than in the neutral precursor.[3]

## Synthesis

According to the original synthesis by Calderazzo, V(CO)6 is prepared in two-steps via the intermediacy of V(CO)−6. In the first step, VCl3 is reduced with metallic sodium under 200 atm CO at 160 °C. The solvent for this reduction is typically diglyme, CH3OCH2CH2OCH2CH2OCH3. This triether solubilizes sodium salts, akin to the behavior of a crown ether:

4 Na + VCl3 \+ 6 CO + 2 diglyme → [Na(diglyme)2][V(CO)6] + 3 NaCl

The resulting anion is oxidized with acid:[4]

2 V(CO)−6 \+ 2 H3PO4 → 2 V(CO)6 \+ H2 \+ 2 H2PO−4

## Reactions

Vanadium hexacarbonyl is thermally unstable. Its primary reaction is reduction to the monoanion V(CO)−6, salts of which are well studied. It is also susceptible to substitution by tertiary phosphine ligands, often leading to disproportionation.

V(CO)6 reacts with sources of the cyclopentadienyl anion to give the orange four-legged piano stool complex (C5H5)V(CO)4 (m.p. 136 °C). Like many charge-neutral organometallic compounds, this half-sandwich species is volatile. In the original preparation of this species, C5H5HgCl was employed as the source of C5H−5.

## References

1. ↑ PubChem. "Vanadium carbonyl" (in en). https://pubchem.ncbi.nlm.nih.gov/compound/6097005.
2. ↑ Elschenbroich, C.; Salzer, A. (1992). Organometallics: A Concise Introduction (2nd ed.). Weinheim: Wiley-VCH. ISBN 3-527-28165-7.
3. ↑ Bellard, S.; Rubinson, K. A.; Sheldrick, G. M. (1979). "Crystal and Molecular Structure of Vanadium Hexacarbonyl". Acta Crystallographica B35 (2): 271–274. doi:10.1107/S0567740879003332. Bibcode: 1979AcCrB..35..271B.
4. ↑ Liu, X.; Ellis, J. E. (2004). Hexacarbonylvanadate(1−) and Hexacarbonylvanadium(0). 34. 96–103. doi:10.1002/0471653683.ch3. ISBN 0-471-64750-0.

## Further reading

* Original synthesis: Ercoli, R.; Calderazzo, F.; Alberola, A. (1960). "Synthesis of Vanadium Hexacarbonyl". J. Am. Chem. Soc. 81 (11): 2966–2967. doi:10.1021/ja01496a073. Bibcode: 1960JAChS..82.2966E.

* v
* t
* e

Vanadium compounds

Vanadium(0)|

* V(CO)6

Vanadium(II)|

* VBr2
* VCl2
* VO
* VS

Vanadium(III)|

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

Vanadium(IV)|

* VC
* VO2
* VS2
* VCl4
* VF4

| Organovanadium(IV) compounds|

* VO(C5H7O2)2

|

Vanadyl(IV) compounds|

* VOSO4

Vanadium(V)|

* V2O5
* VOCl3
* VOF3
* VF5
* V2S5

| Vanadyl(V) compounds|

* VO(ClO4)3

|

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