Gallium trichloride

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Gallium trichloride
Gallium-trichloride-from-xtal-2004-3D-balls.png
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Names
Other names
Gallium(III) chloride, Trichlorogallium, Trichlorogallane
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.268 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
RTECS number
  • LW9100000
UNII
  • InChI=1S/3ClH.Ga/h3*1H;/q;;;+3/p-3 Yes check.svgY
    Key: UPWPDUACHOATKO-UHFFFAOYSA-K Yes check.svgY
  • InChI=1/3ClH.Ga/h3*1H;/q;;;+3/p-3
    Key: UPWPDUACHOATKO-DFZHHIFOAO
  • monomer:Cl[Ga](Cl)Cl
  • dimer:Cl[Ga-]1(Cl)[Cl+] [Ga-]([Cl+]1)(Cl)Cl
Properties
GaCl
3
Molar mass 176.073 g/mol
Appearancecolorless crystals
deliquescent
Density 2.47 g/cm3
2.053 g/cm3 at melting point
Melting point 77.9 °C (172.2 °F; 351.0 K) (anhydrous)
44.4 °C (hydrate)
Boiling point 201 °C (394 °F; 474 K)
very soluble
Solubility soluble in benzene, CCl4, CS2
−63.0·10−6 cm3/mol
Hazards
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
3
0
1
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
4700 mg/kg (rat, oral)
Related compounds
Other anions
Gallium(III) fluoride
Gallium(III) bromide
Gallium(III) iodide
Other cations
Aluminium chloride
Indium(III) chloride
Thallium(III) chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Gallium trichloride is the chemical compound with the formula GaCl3. Solid gallium trichloride exists as a dimer with the formula Ga2Cl6. [1] It is colourless and soluble in virtually all solvents, even alkanes, which is truly unusual for a metal halide. It is the main precursor to most derivatives of gallium and a reagent in organic synthesis. [2]

Contents

As a Lewis acid, GaCl3 is milder than aluminium trichloride. Gallium(III) is easier to reduce than Al(III), so the chemistry of reduced gallium compounds is more extensive than for aluminium. Ga2Cl4 is known whereas the corresponding Al2Cl4 is not. The coordination chemistry of Ga(III) and Fe(III) are similar, and gallium(III) compounds have been used as diamagnetic analogues of ferric compounds.

Preparation

Gallium trichloride can be prepared from the elements, heating gallium metal in a stream of chlorine, and purifying the product by sublimation under vacuum. [3] [4]

2 Ga + 3 Cl2 → 2 GaCl3

It can also be prepared from by heating gallium oxide with thionyl chloride: [5]

Ga2O3 + 3 SOCl2 → 2 GaCl3 + 3 SO2

Gallium metal reacts slowly with hydrochloric acid. This reaction produces hydrogen gas slowly.

Structure

As a solid, it adopts a bitetrahedral structure with two bridging chlorides. Its structure resembles that of aluminium tribromide. In contrast AlCl3 and InCl3 feature contain 6 coordinate metal centers. As a consequence of its molecular nature and associated low lattice energy, gallium trichloride has a lower melting point vs the aluminium and indium trihalides. The formula of Ga2Cl6 is often written as Ga2(μ-Cl)2Cl4. In the gas phase the dimers dissociate to trigonal planar monomers.[ citation needed ]

Complexes

Gallium is the lightest member of Group 13 to have a full d shell, (gallium has the electronic configuration [ Ar] 3d10 4s2 4p1) below the valence electrons that could take part in d-π bonding with ligands. The low oxidation state of Ga in Ga(III)Cl3, along with the low electronegativity and high polarisability, allow GaCl3 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:

With a chloride ion as ligand the tetrahedral GaCl4 ion is produced, the 6 coordinate GaCl63 cannot be made. Compounds like KGa2Cl7 that have a chloride bridged anion are known. [6] In a molten mixture of KCl and GaCl3, the following equilibrium exists:

2 GaCl4 Ga2Cl7 + Cl

Uses

Organic synthesis

Gallium trichloride is a Lewis acid catalyst, such as in the Friedel–Crafts reaction, and is also used in carbogallation reactions of compounds with a carbon-carbon triple bond. It is a precursor to organogallium reagents. It is also used as a catalyst in many organic reactions. [2]

Detection of solar neutrinos

110 tons of gallium trichloride 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. [7]

See also

Related Research Articles

<span class="mw-page-title-main">Gallium</span> Chemical element, symbol Ga and atomic number 31

Gallium is a chemical element with the symbol Ga and atomic number 31. Discovered by the French chemist Paul-Émile Lecoq de Boisbaudran in 1875, gallium is in group 13 of the periodic table and is similar to the other metals of the group.

Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are some of the most important and commonplace compounds of iron. They are available both in anhydrous and in hydrated forms which are both hygroscopic. They feature iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while all forms are mild oxidizing agent. It is used as a water cleaner and as an etchant for metals.

<span class="mw-page-title-main">Titanium tetrachloride</span> Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as "tickle" or "tickle 4" due to the phonetic resemblance of its molecular formula to the word.

<span class="mw-page-title-main">Cerium(III) chloride</span> Chemical compound

Cerium(III) chloride (CeCl3), also known as cerous chloride or cerium trichloride, is a compound of cerium and chlorine. It is a white hygroscopic salt; it rapidly absorbs water on exposure to moist air to form a hydrate, which appears to be of variable composition, though the heptahydrate CeCl3·7H2O is known. It is highly soluble in water, and (when anhydrous) it is soluble in ethanol and acetone.

<span class="mw-page-title-main">Aluminium chloride</span> Chemical compound

Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula AlCl3. It forms a hexahydrate with the formula [Al(H2O)6]Cl3, containing six water molecules of hydration. Both the anhydrous form and the hexahydrate are colourless crystals, but samples are often contaminated with iron(III) chloride, giving them a yellow colour.

<span class="mw-page-title-main">Chromium(III) chloride</span> Chemical compound

Chromium(III) chloride (also called chromic chloride) is an inorganic chemical compound with the chemical formula CrCl3. It forms several hydrates with the formula CrCl3·nH2O, among which are hydrates where n can be 5 (chromium(III) chloride pentahydrate CrCl3·5H2O) or 6 (chromium(III) chloride hexahydrate CrCl3·6H2O). The anhydrous compound with the formula CrCl3 are violet crystals, while the most common form of the chromium(III) chloride are the dark green crystals of hexahydrate, CrCl3·6H2O. Chromium chlorides find use as catalysts and as precursors to dyes for wool.

<span class="mw-page-title-main">Rhodium(III) chloride</span> Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic solids featuring octahedral Rh(III) centres. Depending on the value of n, the material is either a dense brown solid or a soluble reddish salt. The soluble trihydrated (n = 3) salt is widely used to prepare compounds used in homogeneous catalysis, notably for the industrial production of acetic acid and hydroformylation.

<span class="mw-page-title-main">Gold(III) chloride</span> Chemical compound

Gold(III) chloride, traditionally called auric chloride, is an inorganic compound of gold and chlorine with the molecular formula Au2Cl6. The "III" in the name indicates that the gold has an oxidation state of +3, typical for many gold compounds. It has two forms, the monohydrate (AuCl3·H2O) and the anhydrous form, which are both hygroscopic and light-sensitive solids. This compound is a dimer of AuCl3. This compound has a few uses, such as an oxidizing agent and for catalyzing various organic reactions.

<span class="mw-page-title-main">Scandium chloride</span> Chemical compound

Scandium(III) chloride is the inorganic compound with the formula ScCl3. It is a white, high-melting ionic compound, which is deliquescent and highly water-soluble. This salt is mainly of interest in the research laboratory. Both the anhydrous form and hexahydrate (ScCl3•6H2O) are commercially available.

Boron trichloride is the inorganic compound with the formula BCl3. This colorless gas is a reagent in organic synthesis. It is highly reactive toward water.

Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins.

<span class="mw-page-title-main">Molybdenum(V) chloride</span> Chemical compound

Molybdenum(V) chloride is the inorganic compound with the empirical formula MoCl5. This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents.

<span class="mw-page-title-main">Indium(III) chloride</span> Chemical compound

Indium(III) chloride is the chemical compound with the formula InCl3. This salt is a white, flaky solid with applications in organic synthesis as a Lewis acid. It is also the most available soluble derivative of indium. This is one of three known indium chlorides.

<span class="mw-page-title-main">Gallium(III) bromide</span> Chemical compound

Gallium(III) bromide (GaBr3) is a chemical compound, and one of four gallium trihalides.

There are three sets of gallium halides, the trihalides where gallium has oxidation state +3, the intermediate halides containing gallium in oxidation states +1, +2 and +3 and some unstable monohalides, where gallium has oxidation state +1.

<span class="mw-page-title-main">Niobium(IV) chloride</span> Chemical compound

Niobium(IV) chloride, also known as niobium tetrachloride, is the chemical compound of formula NbCl4. This compound exists as dark violet crystals, is highly sensitive to air and moisture, and disproportiates into niobium(III) chloride and niobium(V) chloride when heated.

<span class="mw-page-title-main">Organogallium chemistry</span> Chemistry of Organogallium compounds

Organogallium chemistry is the chemistry of organometallic compounds containing a carbon to gallium (Ga) chemical bond. Despite their high toxicity, organogallium compounds have some use in organic synthesis. The compound trimethylgallium is of some relevance to MOCVD as a precursor to gallium arsenide via its reaction with arsine at 700 °C:

<span class="mw-page-title-main">Metal halides</span>

Metal halides are compounds between metals and halogens. Some, such as sodium chloride are ionic, while others are covalently bonded. A few metal halides are discrete molecules, such as uranium hexafluoride, but most adopt polymeric structures, such as palladium chloride.

<span class="mw-page-title-main">Aluminium compounds</span>

Aluminium (or aluminum) combines characteristics of pre- and post-transition metals. Since it has few available electrons for metallic bonding, like its heavier group 13 congeners, it has the characteristic physical properties of a post-transition metal, with longer-than-expected interatomic distances. Furthermore, as Al3+ is a small and highly charged cation, it is strongly polarizing and aluminium compounds tend towards covalency; this behaviour is similar to that of beryllium (Be2+), an example of a diagonal relationship. However, unlike all other post-transition metals, the underlying core under aluminium's valence shell is that of the preceding noble gas, whereas for gallium and indium it is that of the preceding noble gas plus a filled d-subshell, and for thallium and nihonium it is that of the preceding noble gas plus filled d- and f-subshells. Hence, aluminium does not suffer the effects of incomplete shielding of valence electrons by inner electrons from the nucleus that its heavier congeners do. Aluminium's electropositive behavior, high affinity for oxygen, and highly negative standard electrode potential are all more similar to those of scandium, yttrium, lanthanum, and actinium, which have ds2 configurations of three valence electrons outside a noble gas core: aluminium is the most electropositive metal in its group. Aluminium also bears minor similarities to the metalloid boron in the same group; AlX3 compounds are valence isoelectronic to BX3 compounds (they have the same valence electronic structure), and both behave as Lewis acids and readily form adducts. Additionally, one of the main motifs of boron chemistry is regular icosahedral structures, and aluminium forms an important part of many icosahedral quasicrystal alloys, including the Al–Zn–Mg class.

Gallium compounds are compounds containing the element gallium. These compounds are found primarily in the +3 oxidation state. The +1 oxidation state is also found in some compounds, although it is less common than it is for gallium's heavier congeners indium and thallium. For example, the very stable GaCl2 contains both gallium(I) and gallium(III) and can be formulated as GaIGaIIICl4; in contrast, the monochloride is unstable above 0 °C, disproportionating into elemental gallium and gallium(III) chloride. Compounds containing Ga–Ga bonds are true gallium(II) compounds, such as GaS (which can be formulated as Ga24+(S2−)2) and the dioxan complex Ga2Cl4(C4H8O2)2. There are also compounds of gallium with negative oxidation states, ranging from -5 to -1, most of these compounds being magnesium gallides (MgxGay).

References

  1. Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN   0-19-855370-6.
  2. 1 2 Yamaguchi, Masahiko; Matsunaga, Shigeki; Shibasaki, Masakatsu; Michelet, Bastien; Bour, Christophe; Gandon, Vincent (2014), "Gallium Trichloride", Encyclopedia of Reagents for Organic Synthesis, John Wiley & Sons, Ltd, pp. 1–8, doi:10.1002/047084289x.rn00118u.pub3, ISBN   9780470842898
  3. S.C. Wallwork I.J.Worral J.Chem. Soc 1965,1816
  4. Kovar, R. A. "Gallium Trichloride" Inorganic Syntheses, 1977, volume XVII, pp 167-172. ISBN   0-07-044327-0
  5. H.Hecht, G.Jander, H.Schlapmann Z. Anorg. Allgem. Chem. Vol.254, p.255 (1947)
  6. J H von Barner Inorg Chem 1985 24 1686
  7. David R. Lide, ed. Handbook of Chemistry and Physics, 85th Edition, Internet Version 2005. CRC Press, 2005.