Vanadium carbonyl

Vanadium carbonyl

Chembox new
Name = Vanadium carbonyl
ImageFile = V(CO)6.png ImageSize = 200px
ImageName = Vanadium carbonyl
IUPACName = hexacarbonylvanadium(0)
OtherNames = vanadium carbonyl
Section1 = Chembox Identifiers
CASNo = 20644-87-5
RTECS =
Section2 = Chembox Properties
Formula = C6O6V
MolarMass = 219.00 g/mol
Appearance = blue-green crystals
yellow solutions
Density =
Solubility = insoluble
Solvent = other solvents
SolubleOther = 5 g/L hexane; more soluble in dichloromethane
MeltingPt = decomp
BoilingPt = sublimes 50 °C (15 mm Hg)
Section3 = Chembox Structure
Coordination = octahedral
CrystalStruct = orthorhombic
Dipole = 0 D
Section7 = Chembox Hazards
ExternalMSDS =
MainHazards = CO source
RPhrases =
SPhrases =
Section8 = Chembox Related
Function = compounds
OtherFunctn = Cr(CO)6, [V(CO)6] -, VCl3

Vanadium carbonyl, also known as vanadium hexacarbonyl, is the chemical compound with the formula V(CO)6. This highly reactive species is noteworthy from theoretical and scholarly perspectives. It is a rare isolable homoleptic metal carbonyl that is paramagnetic. Most species with the formula Mx(CO)y follow the 18e rule, whereas V(CO)6 has 17 valence electrons. [C. Elschenbroich, A. Salzer ”Organometallics : A Concise Introduction” (2nd Ed) (1992) from Wiley-VCH: Weinheim. ISBN 3-527-28165-7]

ynthesis

Traditionally 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 NaClAn improved low pressure synthesis has been developed. [Liu, X.; Ellis, J. E.; "Hexacarbonylvanadate(1−) and Hexacarbonylvanadium(0)" Inorganic Syntheses 2004, volume 34, pages 96-103. ISBN 0-471-64750-0]

Reactions

The most characteristic reaction for V(CO)6 is a thermally sensitive material. 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-coloured 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 C5H5.

tructure

V(CO)6 adopts an octahedral coordination geometry. High resolution X-ray crystallography indicates that the molecule is slightly distorted with two (trans) shorter V-C distances of 1.993 (2) vs. four (equatorial) 2.005 (2) Å. [Bellard, S.; Rubinson, K. A.; Sheldrick, G. M. "Crystal and molecular structure of vanadium hexacarbonyl" Acta Crystallographica1979. volume B35, pages 271-274 doi|10.1107/S0567740879003332] Such a distortion could be due to a Jahn-Teller effect.

References

Further reading

* Original synthesis: Calderazzo, F.; Ercoli, R., "Synthesis of V(CO)6 and Hexacarbonyl Vanadates" Chimica e l'Industria 1962, volume 44, 990-6.


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