Vanadium(III) chloride

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
CAS Number	7718-98-1 ;
3D model (JSmol)	Interactive image;
ChemSpider	10801024 ;
ECHA InfoCard	100.028.859
PubChem CID	62647;
RTECS number	YW2800000;
CompTox Dashboard (EPA)	DTXSID3064776 ;
	InChI InChI=1S/3ClH.V/h31H;/q;;;+3/p-3 Key: HQYCOEXWFMFWLR-UHFFFAOYSA-K ; InChI=1/3ClH.V/h31H;/q;;;+3/p-3 Key: HQYCOEXWFMFWLR-DFZHHIFOAB;
	SMILES [V+3].[Cl-].[Cl-].[Cl-];
Properties
Chemical formula	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)
Solubility in water	soluble
Magnetic susceptibility (χ)	+3030.0·10−6 cm3/mol
Structure
Crystal structure	Trigonal, hR24
Space group	R-3, No. 148
Hazards
Safety data sheet	Vanadium(III) Chloride
GHS pictograms	[1]
GHS Signal word	Danger[1]
GHS hazard statements	H302, H314[1]
GHS precautionary statements	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

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

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

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] Vanadium(III) chloride reacts with acetonitrile to give the green adduct VCl₃(MeCN)₃. When treated with KCN, VCl₃ converts to [V(CN)₇]⁴⁻ (early metals commonly adopt coordination numbers greater 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.

Organometallic derivatives

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

"Vanadium(III) Chloride SDS". American Elements. Retrieved 2018-08-17.
Holleman, A. F.; Wiberg, E. Inorganic Chemistry Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
Young, R. C.; Smith, M. E. "Vanadium(III) Chloride" Inorganic Syntheses volume IV, page 128–130, 1953. doi:10.1002/9780470132357.ch43
G. Brauer (1963). "Vanadium Oxydichloride". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. NY: Academic Press. p. 1263.
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
Donovan, William F.; Smith, Peter W. (1975). "Crystal and Molecular Structures of Aquahalogenovanadium(III) Complexes. Part I. X-Ray Crystal Structure of trans-Tetrakisaquadibromo-Vanadium(III) Bromide Dihydrate and the Isomorphous Chloro- Compound". Journal of the Chemical Society, Dalton Transactions (10): 894. doi:10.1039/DT9750000894.
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)
Manzer, L. E. (1982). Tetrahydrofuran Complexes of Selected Early Transition Metals. Inorganic Syntheses. 21. pp. 135–140. doi:10.1002/9780470132524.ch31.
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

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[SDS-1] "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

[VX3aq6-6] Donovan, William F.; Smith, Peter W. (1975). "Crystal and Molecular Structures of Aquahalogenovanadium(III) Complexes. Part I. X-Ray Crystal Structure of trans-Tetrakisaquadibromo-Vanadium(III) Bromide Dihydrate and the Isomorphous Chloro- Compound". Journal of the Chemical Society, Dalton Transactions (10): 894. 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. (1982). Tetrahydrofuran Complexes of Selected Early Transition Metals. Inorganic Syntheses. 21. pp. 135–140. doi:10.1002/9780470132524.ch31.

[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