zirconium tetrachloride

Zirconium(IV) chloride, also known as zirconium tetrachloride, () is an inorganic compound frequently used as a precursor to other compounds of zirconium. This white high-melting solid hydrolyzes rapidly in humid air.

Structure

Unlike molecular TiCl₄, solid ZrCl₄ adopts a polymeric structure wherein each Zr is octahedrally coordinated. This difference in structures is responsible for the disparity in their properties: is distillable, but is a solid. In the solid state, ZrCl₄ adopts a tape-like linear polymeric structure—the same structure adopted by HfCl₄. This polymer degrades readily upon treatment with Lewis bases, which cleave the Zr-Cl-Zr linkages.

Synthesis

This conversion entails treatment of the oxide with carbon as the oxide "getter" in the presence of chlorine at high temperature:
:ZrO₂ + 2 C + 2 Cl₂ → ZrCl₄ + 2 CO

A laboratory scale process uses carbon tetrachloride in place of carbon and chlorine:
:ZrO₂ + 2 CCl₄ → ZrCl₄ + 2 COCl₂

Applications

Precursor to Zr metal

ZrCl₄ is an intermediate in the conversion of zirconium minerals to metallic zirconium by the Kroll process. In nature, zirconium minerals invariably exist as oxides (reflected also by the tendency of all zirconium chlorides to hydrolyze). For their conversion to bulk metal, these refractory oxides are first converted to the tetrachloride, which can be distilled at high temperatures. The purified ZrCl₄ can be reduced with Zr metal to produce zirconium(III) chloride.

Other uses

ZrCl₄ is the most common precursor for chemical vapor deposition of zirconium dioxide and zirconium diboride.

In organic synthesis zirconium tetrachloride is used as a weak Lewis acid for the Friedel-Crafts reaction, the Diels-Alder reaction and intramolecular cyclisation reactions. It is also used to make water-repellent treatment of textiles and other fibrous materials.

Properties and reactions

Hydrolysis of ZrCl₄ gives the hydrated hydroxy chloride cluster called zirconyl chloride. This reaction is rapid and virtually irreversible, consistent with the high oxophilicity of zirconium(IV). For this reason, manipulations of ZrCl₄ typically require air-free techniques.

ZrCl₄ is the principal starting compound for the synthesis of many organometallic complexes of zirconium. Because of its polymeric structure, ZrCl₄ is usually converted to a molecular complex before use. It forms a 1:2 complex with tetrahydrofuran: CAS 1959-01-3 mp 175–177 °C. Sodium cyclopentadienide (NaC₅H₅) reacts with ZrCl₄(THF)₂ to give zirconocene dichloride, ZrCl₂(C₅H₅)₂, a versatile organozirconium complex. One of the most curious properties of ZrCl₄ is its high solubility in the presence of methylated benzenes, such as durene. This solubilization arises through the formation of π-complexes.

The log (base 10) of the vapor pressure of zirconium tetrachloride (from 480 to 689 K) is given by the equation: log₁₀(P) = −5400/T + 11.766, where the pressure is measured in torrs and temperature in kelvins. The log (base 10) of the vapor pressure of solid zirconium tetrachloride (from 710 to 741 K) is given by the equation log₁₀(P) = −3427/T + 9.088. The pressure at the melting point is 14,500 torrs.

References

{{Chlorides

Zirconium(IV) compounds
Chlorides
Metal halides
Coordination complexes