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Vanadium tetrachloride

Vanadium tetrachloride is the inorganic compound with the formula VCl<sub>4</sub>. This reddish-brown liquid serves as a useful reagent for the preparation of other vanadium compounds.

Synthesis, bonding, basic properties

With one more valence electron than diamagnetic TiCl<sub>4</sub>, VCl<sub>4</sub> is a paramagnetic liquid. It is one of only a few paramagnetic compounds that is liquid at room temperature.

VCl<sub>4</sub> is prepared by chlorination of vanadium metal. VCl<sub>5</sub> does not form in this reaction; Cl<sub>2</sub> lacks the oxidizing power to attack VCl<sub>4</sub>. VCl<sub>5</sub> can however be prepared indirectly from VF<sub>5</sub> at −78&nbsp;°C.

Reactions

Consistent with its high oxidizing power, VCl<sub>4</sub> reacts with HBr at -50&nbsp;°C to produce VBr<sub>3</sub>. The reaction proceeds via VBr<sub>4</sub>, which releases Br<sub>2</sub> during warming to room temperature.

2&nbsp;VCl<sub>4</sub> + 8&nbsp;HBr → 2&nbsp;VBr<sub>3</sub> + 8&nbsp;HCl + Br<sub>2</sub>

VCl<sub>4</sub> forms adducts with many donor ligands, for example, VCl<sub>4</sub>(THF)<sub>2</sub>.

It is the precursor to vanadocene dichloride.

Organic chemistry

In organic synthesis, VCl<sub>4</sub> is used for the oxidative coupling of phenols. For example, it converts phenol into a mixture of 4,4'-, 2,4'-, and 2,2'-biphenols:

2&nbsp;C<sub>6</sub>H<sub>5</sub>OH + 2&nbsp;VCl<sub>4</sub> → HOC<sub>6</sub>H<sub>4</sub>–C<sub>6</sub>H<sub>4</sub>OH + 2&nbsp;VCl<sub>3</sub> + 2&nbsp;HCl

Applications

VCl<sub>4</sub> is a catalyst for the polymerization of alkenes, especially those useful in the rubber industry. The underlying technology is related to Ziegler–Natta catalysis, which involves the intermediacy of vanadium alkyls.

References