Gallium trichloride

Gallium(III) chloride is an inorganic chemical compound with the formula which forms a monohydrate, . Solid gallium(III) chloride is a deliquescent colorless crystals and exists as a dimer with the formula . It is colourless and soluble in virtually all solvents, even alkanes, which is unusual for a metal halide. It is the main precursor to most derivatives of gallium and a reagent in organic synthesis.

As a Lewis acid, is milder than aluminium chloride. It is also easier to reduce than aluminium chloride. The coordination chemistry of Ga(III) and Fe(III) are similar, so gallium(III) chloride has been used as a diamagnetic analogue of ferric chloride.

Preparation

Gallium(III) chloride can be prepared from the elements by heating gallium metal in a stream of chlorine at 200 °C and purifying the product by sublimation under vacuum.

:

It can also be prepared from by heating gallium oxide with thionyl chloride:
:

Gallium metal reacts slowly with hydrochloric acid, producing hydrogen gas. Evaporation of this solution produces the monohydrate.

Structure

As a solid, it adopts a bitetrahedral structure with two bridging chlorides. Its structure resembles that of aluminium tribromide. In contrast and feature contain 6 coordinate metal centers. As a consequence of its molecular nature and associated low lattice energy, gallium(III) chloride has a lower melting point vs the aluminium and indium(III) halides. The formula of is often written as .

In the gas-phase, the dimeric () and trigonal planar monomeric () are in a temperature-dependent equilibrium, with higher temperatures favoring the monomeric form. At 870 K, all gas-phase molecules are effectively in the monomeric form.

In the monohydrate, the gallium is tetrahedrally coordinated with three chlorine molecules and one water molecule.

Properties

Physical

Gallium(III) chloride is a diamagnetic and deliquescent colorless solid that melts at 77.9 °C and boils at 201 °C without decomposition to the elements. This low melting point results from the fact that it forms discrete molecules in the solid state. Gallium(III) chloride dissolves in water with the release of heat to form a colorless solution, which when evaporated, produces a colorless monohydrate, which melts at 44.4 °C.

Chemical

Gallium is the lightest member of Group 13 to have a full ''d'' shell, (gallium has the electronic configuration Ar">Argon.html" ;"title="nowiki/>Argon">Ar3''d''¹⁰ 4''s''² 4''p''¹) below the valence electrons that could take part in ''d'' shell Pi bond, π bonding with ligands.
The low oxidation state of Ga in , along with the low electronegativity and high polarisability, allow to behave as a "soft acid" in terms of the HSAB theory. The strength of the bonds between gallium halides and ligands have been extensively studied. What emerges is:
* is a weaker Lewis acid than towards N and O donors, e.g. pyridine
* is a stronger Lewis acid than towards thioethers e.g. dimethyl sulfide,
With a chloride ion as ligand the tetrahedral tetrachlorogallate(III) ion is produced, the 6 coordinate cannot be made. Compounds like that have a chloride bridged anion are known.
In a molten mixture of KCl and , the following equilibrium exists:
:
When dissolved in water, gallium(III) chloride dissociates into the octahederal and ions forming an acidic solution, due to the hydrolysis of the hexaaquogallium(III) ion:
: (''pK_a'' = 3.0)
In basic solution, it hydrolyzes to gallium(III) hydroxide, which redissolves with the addition of more hydroxide, possibly to form .

Uses

Organic synthesis

Gallium(III) chloride is a Lewis acid catalyst, such as in the Friedel–Crafts reaction, which is able to substitute more common lewis acids such as ferric chloride. Gallium complexes strongly with π-donors, especially silylethynes, producing a strongly electrophilic complex. These complexes are used as an alkylating agent for aromatic hydrocarbons.

It is also used in carbogallation reactions of compounds with a carbon-carbon triple bond. It is also used as a catalyst in many organic reactions.

Organogallium compounds

It is a precursor to organogallium reagents. For example, trimethylgallium, an organogallium compound used in MOCVD to produce various gallium-containing semiconductors, is produced by the reaction of gallium(III) chloride with various alkylating agents, such as dimethylzinc, trimethylaluminium, or methylmagnesium iodide.

Purification of gallium

Gallium(III) chloride is an intermediate in various gallium purification processes, where gallium(III) chloride is fractionally distilled or extracted from acid solutions.

Detection of solar neutrinos

110 tons of gallium(III) chloride aqueous solution was used in the GALLEX and GNO experiments performed at Laboratori Nazionali del Gran Sasso in Italy to detect solar neutrinos. In these experiments, germanium-71 was produced by neutrino interactions with the isotope gallium-71 (which has a natural abundance of 40%), and the subsequent beta decays of germanium-71 were measured.David R. Lide, ed. ''Handbook of Chemistry and Physics, 85th Edition'', Internet Version 2005. CRC Press, 2005.

See also

* Gallium halides

References

Further reading

*

External links

*

{{DEFAULTSORT:Gallium Trichloride
Inorganic compounds
Gallium compounds
Chlorides
Metal halides