Vanadium oxytrichloride


Vanadium oxytrichloride is the inorganic compound with the formula VOCl3. This yellow distillable liquid hydrolyzes readily in air. It is an oxidizing agent. It is used as a reagent in organic synthesis. Samples often appear red or orange owing to an impurity of vanadium tetrachloride.

Properties

VOCl3 is a vanadium compound with vanadium in the +5 oxidation state and as such is diamagnetic. It is tetrahedral with O-V-Cl bond angles of 111° and Cl-V-Cl bond angles of 108°. The V-O and V-Cl bond lengths are 157 and 214 pm, respectively. VOCl3 is highly reactive toward water and evolves HCl upon standing. It is soluble in nonpolar solvents such as benzene, CH2Cl2, and hexane. In some aspects, the chemical properties of VOCl3 and POCl3 are similar. One distinction is that VOCl3 is a strong oxidizing agent, whereas the phosphorus compound is not. Neat VOCl3 is the usual chemical shift standard for 51V NMR spectroscopy.

Preparation

VOCl3 arises by the chlorination of V2O5. The reaction proceeds near 600 °C:
Heating an intimate mixture of V2O5, chlorine, and carbon at 200–400 °C also gives VOCl3. In this case the carbon serves as a deoxygenation agent akin to its use in the chloride process for the manufacturing of TiCl4 from TiO2.
Vanadium oxide can also be used as a precursor:
A more typical laboratory synthesis involves the chlorination of V2O5 using SOCl2.

Reactions

Hydrolysis and alcoholysis

VOCl3 quickly hydrolyzes resulting in vanadium pentoxide and hydrochloric acid. In the picture, orange V2O5 can be seen forming on the walls of the beaker. An intermediate in this process is VO2Cl:
VOCl3 reacts with alcohols especially in the presence of a proton-acceptor to give alkoxides, as illustrated by this synthesis of vanadyl isopropoxide:

Interconversions to other V-O-Cl compounds

VOCl3 is also used in the synthesis of vanadium oxydichloride.
VO2Cl can be prepared by an unusual reaction involving Cl2O.
At >180 °C, VO2Cl decomposes to V2O5 and VOCl3.
Similarly, VOCl2 also decomposes to give VOCl3, together with VOCl.

Adduct formation

VOCl3 is strongly Lewis acidic, as demonstrated by its tendency to form adducts with various bases such as acetonitrile and amines. In forming the adducts, vanadium changes from four-coordinate tetrahedral geometry to six-coordinate octahedral geometry:

VOCl3 in alkene polymerization

VOCl3 is used as a catalyst or precatalytst in production of ethylene-propylene rubbers.