Vanadium(III) chloride

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Vanadium(III) chloride
Plan view of a single layer in the crystal structure of vanadium(III) chloride
Layer stacking in the crystal structure of vanadium(III) chloride
Names
IUPAC names
Vanadium(III) chloride
Vanadium trichloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.028.859
RTECS number
  • YW2800000
Properties
VCl3
Molar mass 157.30 g/mol
Appearance violet crystals
paramagnetic
Density 3.0 g/cm3 (20 °C)
Melting point > 300 °C (572 °F; 573 K) (decomposes)
soluble
+3030.0·10−6 cm3/mol
Structure
Trigonal, hR24
R-3, No. 148
Hazards
Safety data sheet Vanadium(III) Chloride
GHS pictograms GHS05: CorrosiveGHS07: Harmful[1]
GHS Signal word Danger[1]
H302, H314[1]
P280, P305, P351, P338, P310[1]
Flash point Non-flammable
Related compounds
Other anions
vanadium trifluoride, vanadium(III) sulfide, vanadium tribromide
Other cations
titanium trichloride, chromium(III) chloride, niobium trichloride, tantalum trichloride
Related compounds
vanadium dichloride, vanadium tetrachloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Vanadium trichloride is the inorganic compound with the formula VCl3. This purple salt is a common precursor to other vanadium(III) complexes.[2]

Structure[edit]

VCl3 has the common BiI3 structure, a motif that features hexagonally closest-packed chloride framework with vanadium ions occupying the octahedral holes. VBr3 and VI3 adopt the same structure, but VF3 features a structure more closely related to ReO3. VCl3 is paramagnetic and has two unpaired electrons.

Preparation and reactions[edit]

VCl3 is prepared by heating VCl4 at 160–170 °C under a flowing stream of inert gas, which sweeps out the Cl2. The bright red liquid converts to a purple solid.

Heating of VCl3 decomposes with volatilization of VCl4, leaving VCl2.[3] Upon heating under H2 at 675 °C (but less than 700 °C), VCl3 reduces to greenish VCl2.

2 VCl3 + H2 → 2 VCl2 + 2 HCl

Comproportionation of vanadium trichloride and vanadium(V) oxides gives vanadium oxydichloride:[4]

V2O5 + VOCl3 + 3 VCl3 → 6 VOCl2

Vanadium trichloride catalyses the pinacol coupling reaction of benzaldehyde (PhCHO) to 1,2-diphenyl-1,2-ethanediol by various reducing metals such as zinc:[5]

Zn + 2 H2O + 2 PhCHO → (PhCH(OH))2 + Zn(OH)2

Complexes[edit]

VCl3 forms colorful adducts and derivatives with a broad scale of ligands. VCl3 dissolves in water to give the hexahydrate, but the formula is deceptive. The salt is described by the formula [VCl2(H2O)4]Cl.2H2O. In other words, two of the water molecules are not bound to the vanadium, whose structure resembles the corresponding Fe(III) derivative. Removal of the two bound chloride ligands from [VCl2(H2O)4]+ in aqueous solution gives the green ion [V(H2O)6]3+.[6]

Structure of VCl3(thf)3.[7]

With tetrahydrofuran, VCl3 forms the red/pink adduct VCl3(THF)3.[8] With acetonitrile, one obtains the green adduct VCl3(MeCN)3.

When treated with KCN, VCl3 converts to [V(CN)7]4−. It is common for early metals to adopt high coordination numbers (more than 6) with compact ligands. Complementarily, larger metals can form complexes with rather bulky ligands. This aspect is illustrated by the isolation of VCl3(NMe3)2, containing two bulky NMe3 ligands.

Precursor to organometallics[edit]

The reactive species V(mesityl)3 forms from VCl3.[9]

VCl3(THF)3 + 3 LiC6H2-2,4,6-Me3 → V(C6H2-2,4,6-Me3)3(THF) + 3 LiCl

This species binds CO and, under appropriate conditions, N2.

References[edit]

  1. ^ a b c d "Vanadium(III) Chloride SDS". American Elements. Retrieved 2018-08-17.
  2. ^ Holleman, A. F.; Wiberg, E. Inorganic Chemistry Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  3. ^ Young, R. C.; Smith, M. E. "Vanadium(III) Chloride" Inorganic Syntheses volume IV, page 128–130, 1953. doi:10.1002/9780470132357.ch43
  4. ^ G. Brauer (1963). "Vanadium Oxydichloride". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. NY: Academic Press. p. 1263.
  5. ^ Vanadium-Catalyzed Pinacol Coupling Reaction in Water Xiaoliang Xu and Toshikazu Hirao J. Org. Chem.; 2005; 70(21) pp 8594–96. doi:10.1021/jo051213f
  6. ^ Donovan, W. F.; Smith, P. W. "Crystal and Molecular Structures of Aquahalogenovanadium(1ii) Complexes. Part 1. X-Ray Crystal Structure of trans-Tetrakisaquadibromovanadium(III) Bromide Dihydrate and the lsomorphous Chloro-compound" Journal of the Chemical Society, Dalton Transactions. 1975, pages 894-896. doi:10.1039/DT9750000894
  7. ^ F.A.Cotton, S.A.Duraj, G.L.Powell, W.J.Roth (1986). "Comparative Structural Studies of the First Row Early Transition Metal(III) Chloride Tetrahydrofuran Solvates". Inorg. Chim. Acta. 113: 81. doi:10.1016/S0020-1693(00)86863-2.CS1 maint: uses authors parameter (link)
  8. ^ Manzer, L. E. "Tetrahydrofuran Complexes of Selected Early Transition Metals," Inorganic Synthesis. 21, 135–140, (1982).
  9. ^ Vivanco, M.; Ruiz, J.; Floriani, C.; Chiesi-Villa, A.; Rizzoli, C. "Chemistry of the vanadium-carbon .sigma. bond. 1. Insertion of carbon monoxide, isocyanides, carbon dioxide, and heterocumulenes into the V-C bond of Tris(mesityl)vanadium(III)" Organometallics 1993 volume 12, 1794–1801. doi:10.1021/om00029a042