Tungsten dichloride dioxide

Tungsten dichloride dioxide, or Tungstyl chloride is the chemical compound with the formula WO2Cl2. It is a yellow-colored solid. It is used as a precursor to other tungsten compounds. Like other tungsten halides, WO2Cl2 is sensitive to moisture, undergoing hydrolysis.

Preparation
WO2Cl2 is prepared by ligand redistribution reaction from tungsten trioxide and tungsten hexachloride:
 * 2 WO3 + WCl6 → 3 WO2Cl2

Using a two-zone tube furnace, a vacuum-sealed tube containing these solids is heated to 350 °C. The yellow product sublimes to the cooler end of the reaction tube. No redox occurs in this process. An alternative route highlights the oxophilicity of tungsten:
 * WCl6 + 2 ((CH3)3Si)2O → 3 WO2Cl2 + 4 (CH3)3SiCl

This reaction, like the preceding one, proceeds via the intermediacy of WOCl4.

Structure
Gaseous tungsten dichloride dioxide is a monomer. Solid tungsten dichloride dioxide is a polymer consisting of distorted octahedral W centres. The polymer is characterized by two short W-O distances, typical for a multiple W-O bond, and two long W-O distances more typical of a single or dative W-O bond.

Related oxy halides
Tungsten forms a number of oxyhalides including WOCl4, WOCl3, WOCl2. The corresponding bromides (WOBr4, WOBr3, WOBr2) are also known as is WO2I2.

Reactions
WO2Cl2 is a Lewis acid, forming soluble adducts of the type WO2Cl2L2, where L is a donor ligand such as bipyridine and dimethoxyethane. Such complexes often cannot be prepared by depolymerization of the inorganic solid, but are generated in situ from WOCl4.