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:
- Ga(CH3)3 + AsH3 → GaAs + 3CH4
Gallium trichloride is an important reagent for the introduction of gallium into organic compounds.
Compounds of the type R3Ga are monomeric. Lewis acidity decreases in the order Al > Ga > In and as a result organogallium compound do not form bridged dimers as organoaluminum compounds do. Organogallium compounds are also less reactive then organoaluminum compounds. They do form stable peroxides.3
- 2Ga + 2Me2Hg → 2Me3Ga + 3 Hg
- GaCl3 + 3MeMgBr → Me3Ga + 3MgBrCl
The electron-deficient nature of gallium can be removed by complex formation, for example
- Me2GaCl + NH3 → [Me2Ga(NH3)Cl]+Cl-
Organogallium compounds are reagents or intermediates in several classes of organic reactions:
- Barbier-type reactions with elemental gallium, allylic substrates and carbonyl compounds
- Carbometallation (carbogallation) reactions 4
The chemistry of organoindium (In) and organothallium (Tl) compounds parallel that of organogallium in many regards. Indium and thallium in oxidation state +1 are more common, for example the metallocenes cyclopentadienylindium(I) and cyclopentadienylthallium. Trimethylindium is important in the semiconductor industry. A special thallium feature is electrophilic thallation of arene compounds, reminiscent of mercuration (the group 12 neighbor). A common reagent for this purpose is thalium(III) trifluoroacetate. The intermediate arylthallium bisfluoroacetate can be isolated and converted to an aryl halide, aryl cyanide, aryl thiol or nitroarene. An example is the iodation of para-xylene.5
A specific niche indium research topic is indium mediated allylation.
- Chemical bonds of carbon with other elements in the periodic table:
|Core organic chemistry||Many uses in chemistry|
|Academic research, but no widespread use||Bond unknown|
- C. Elschenbroich, A. Salzer Organometallics : A Concise Introduction (2nd Ed) (1992) from Wiley-VCH: Weinheim. ISBN 3-527-28165-7
- Chemistry of aluminium, gallium, indium, and thallium Anthony John Downs (Ed.) ISBN 978-0-7514-0103-5 1993
- W, Uhl and M. R. Halvagar et al. (2009). Chemistry-A European Journal (42): 11298–11306. doi:10.1002/chem.200900746.
- GaCl3 in Organic Synthesis Ryo Amemiya and Masahiko Yamaguchi Eur. J. Org. Chem. 2005, 5145–5150 doi:10.1002/ejoc.200500512
- Organic Syntheses, Coll. Vol. 6, p.709 (1988); Vol. 55, p.70 (1976). Link