4/27/2018 Vanadium oxytrichloride - Wikipedia

Vanadium oxytrichloride
Vanadium oxy trichloride is the inorganic compound with the
formula VOCl3 . This y ellow distillable liquid hy droly zes readily in air. It
Vanadium oxytrichloride
is an oxidant. It is used as a reagent in organic sy nthesis. [1] Samples
often appear red or orange owing to an impurity of v anadium
tetrachloride. [2]

Contents
Properties
Preparation
Reactions
Hydrolysis and alcoholysis
Interconversions to other V-O-Cl compounds
Adduct formation
VOCl3 in alkene polymerization

References
Names
IUPAC name
Vanadium trichloride oxide
Properties
Other names
VOCl3 is a v anadium compound with v anadium in the +5 oxidation state
Vanadyl chloride
and as such is diamagnetic. It is tetrahedral with O-V-Cl bond angles of
Vanadyl trichloride
111° and Cl-V-Cl bond angles of 108°. The V-O and V-Cl bond lengths are
157 and 214 pm, respectiv ely . VOCl3 is highly reactiv e toward water Identifiers
and ev olv es HCl upon standing. It is soluble in nonpolar solv ents such as CAS Number 7727-18-6 (http://ww
benzene, CH2 Cl2 , and hexane. In some aspects, the chemical properties
w.commonchemistry.
of VOCl3 and POCl3 are similar. One distinction is that VOCl3 is a strong
org/ChemicalDetail.as
oxidizing agent, whereas the phosphorus compound is not. [3]
px?ref=7727-18-6)
3D model
Preparation (JSmol)
Interactive image (http
s://chemapps.stolaf.e
VOCl3 arises by the chlorination of V 2 O5 . The reaction proceeds near du/jmol/jmol.php?mod
600 °C:[4] el=Cl%5BV%5D%28C
l%29%28Cl%29%3D
3 Cl2 + V2O5 → 2 VOCl3 + 1.5 O2
O)
When the V 2 O5 is used as an intimate mixture with carbon, the ChemSpider 10613097 (http://www.
sy nthesis proceeds at 200–400 °C; in this case the carbon serv es as a chemspider.com/Che
deoxy genation agent akin to its use in the Kroll process for the
mical-Structure.10613
manufacturing of TiCl4 from TiO2 .
097.html)
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4/27/2018 Vanadium oxytrichloride - Wikipedia

Vanadium(III) oxide can also be used as a precursor:[2] ECHA 100.028.892 (https://e

InfoCard cha.europa.eu/substa
3 Cl2 + V2O3 → 2 VOCl3 + 0.5 O2 nce-information/-/subs
tanceinfo/100.028.89
A more ty pical laboratory sy nthesis inv olv es the chlorination of V 2 O5
2)
using SOCl2 . [5]
EC Number 231-780-2
V2O5 + 3 SOCl2 → 2 VOCl3 + 3 SO2 MeSH trichlorooxo+vanadium
(https://www.nlm.nih.g
Reactions ov/cgi/mesh/2014/MB
_cgi?mode=&term=tri
chlorooxo+vanadium)
Hydrolysis and alcoholysis
RTECS YW2975000
Vanadium oxy trichloride quickly hy droly zes resulting in v anadium
number
pentoxide and hy drochloric acid. In the picture, orange V 2 O5 can be
UN number 2443
seen forming on the walls of the beaker. An intermediate in this process
is VO2 Cl: InChI
SMILES
2 VOCl3 + 3 H2O → V2O5 + 6 HCl
Properties
VOCl3 reacts with alcohols especially in the presence of a proton- Chemical VOCl3
acceptor (e.g. Et3 N) to giv e alkoxides: formula
Molar mass 173.300 g mol−1
VOCl3 + 3 ROH → VO(OR)3 + 3 HCl (R = Me, Ph, etc.)
Appearance yellow liquid
Density 1.826 g mL−1
Interconversions to other V-O-Cl compounds
Melting point −76.5 °C (−105.7 °F;
VOCl3 is also used in the sy nthesis of VOCl2 .
196.7 K)
V2O5 + 3 VCl3 + VOCl3 → 6 VOCl2 Boiling point 126.7 °C (260.1 °F;
399.8 K)
Dioxov anadium monochloride can be prepared by an unusual reaction
Solubility in Decomposes
inv olv ing Cl2 O. [6] water

VOCl3 + Cl2O → VO2Cl + 2 Cl2 Vapor 1.84 kPa (at 20 °C)

pressure
At >180 °C, VO2 Cl decomposes to V 2 O5 and VOCl3 . Similarly , VOCl2 Structure
also decomposes to giv e VOCl3 , together with VOCl.
Molecular Tetrahedral
shape
Adduct formation Hazards

VOCl3 is strongly Lewis acidic, as demonstrated by its tendency to form GHS

adducts with v arious bases such as MeCN and amines. In forming the pictograms
adducts, v anadium changes from four-coordinate tetrahedral geometry
GHS signal DANGER
to six-coordinate octahedral geometry :
word
VOCl3 + 2 H2NEt → VOCl3(H2NEt)2 GHS hazard H301, H314
statements

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4/27/2018 Vanadium oxytrichloride - Wikipedia

VOCl3 in alkene polymerization GHS P280, P301+310,

precautionary P305+351+338, P310
VOCl3 is used as a cataly st or precataly tst in production of ethy lene- statements
propy lene rubbers (EPDM).
NFPA 704
1
References 3 3

1. M. O'Brien, B. Vanasse (2001). Encyclopedia of Reagents for Organic

Lethal dose or concentration (LD,
Synthesis.
LC):
2. F. E. Brown, F. A. Griffitts (1939). "Hypovanadous Oxide and Vanadium
Oxytrichloride". Inorg. Syn. I: 106–108. LD50 140 mg kg−1 (oral, rat)
doi:10.1002/9780470132326.ch38 (https://doi.org/10.1002%2F97804701 (median
32326.ch38). dose)
3. A. Earnshaw, N. Greenwood (1997). The Chemistry of the Elements - Related compounds
Second Edition. pp. 513–514.
Related Vanadium(V)
4. A. Holleman, E. Wiberg (from). Inorganic Chemistry. Check date values vanadiums
in: |date= (help) oxytrifluoride
5. G. Brauer "Vanadium oxytrichloride" in Handbook of Preparative Vanadium(V) oxide
Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press,
Except where otherwise noted, data
1963, NY. Vol. 1. p. 1264.
are given for materials in their
6. Oppermann, H. (1967). "Untersuchungen an Vanadinoxidchloriden und standard state (at 25 °C [77 °F],
Vanadinchloriden. I. Gleichgewichte mit VOCl3, VO2Cl und VOCl2". 100 kPa).
Zeitschrift für anorganische und allgemeine Chemie. 351 (3-4): 113–126.
doi:10.1002/zaac.19673510302 (https://doi.org/10.1002%2Fzaac.196735 verify (what is ?)
10302). Infobox references

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