Vanadium hexacarbonyl

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Vanadium hexacarbonyl
Vanadium hexacarbonyl
Identifiers
CAS number 20644-87-5
ChEBI CHEBI:37857 YesY
Properties
Molecular formula C6O6V
Molar mass 219.00 g/mol
Appearance blue-green crystals
yellow solutions
Melting point decomp
Boiling point sublimes 50 °C (15 mm Hg)
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
Related compounds
Related compounds Cr(CO)6, [V(CO)6]-, VCl3
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Vanadium hexacarbonyl is the inorganic 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.[1]

Synthesis[edit]

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 NaCl

The resulting anion is oxidized with acid:

2 [V(CO)6]- + H3PO4 → 2 V(CO)6 + H2 + 2 H2PO4-

An improved low-pressure synthesis has been developed.[2]

Reactions[edit]

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.

Structure[edit]

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.[3] Such a distortion could be due to a Jahn-Teller effect.

References[edit]

  1. ^ C. Elschenbroich, A. Salzer ”Organometallics : A Concise Introduction” (2nd Ed) (1992) from Wiley-VCH: Weinheim. ISBN 3-527-28165-7
  2. ^ Liu, X.; Ellis, J. E.; "Hexacarbonylvanadate(1−) and Hexacarbonylvanadium(0)" Inorganic Syntheses 2004, volume 34, pages 96-103. ISBN 0-471-64750-0
  3. ^ 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

Further reading[edit]

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