Organogallium chemistry

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Trimethylgallium Trimethylgallium-2D.png
Trimethylgallium

Organogallium chemistry is the chemistry of organometallic compounds containing a carbon to gallium (Ga) chemical bond. Despite their high toxicity [ citation needed ], 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:

Contents

Ga(CH3)3 + AsH3 → GaAs + 3CH4

Gallium trichloride is an important reagent for the introduction of gallium into organic compounds.

The main gallium oxidation state is Ga(III), as in all lower group 13 elements (such as aluminium). [1] [2]

Organogallium(III) chemistry

Compounds of the type R3Ga are monomeric. Lewis acidity decreases in the order Al > Ga > In and as a result organogallium compounds do not form bridged dimers as organoaluminum compounds do. Organogallium compounds are also less reactive than organoaluminum compounds. They do form stable peroxides. [3]

Organogallium compounds can be synthesized by transmetallation, for example the reaction of gallium metal with dimethylmercury:

2Ga + 3Me2Hg → 2Me3Ga + 3 Hg

or via organolithium compounds or Grignards:

GaCl3 + 3MeMgBr → Me3Ga + 3MgBrCl

The electron-deficient nature of gallium can be removed by complex formation, for example

Me2GaCl + NH3 → [Me2Ga(NH3)Cl]+Cl

Pi complex formation with alkynes is also known.

Organogallium compounds are reagents or intermediates in several classes of organic reactions:

Higher group 13 organometallic chemistry

Organoindium chemistry and organothallium chemistry 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 thallium(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 iodination of para-xylene. [5]

Arene thallation.svg :

A specific niche indium research topic is indium mediated allylation.

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

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<span class="mw-page-title-main">Organoaluminium chemistry</span>

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Group 2 organometallic chemistry refers to the chemistry of compounds containing carbon bonded to any group 2 element. By far the most common group 2 organometallic compounds are the magnesium-containing Grignard reagents which are widely used in organic chemistry. Other organmetallic group 2 compounds are rare and are typically limited to academic interests.

<span class="mw-page-title-main">Organonickel chemistry</span>

Organonickel chemistry is a branch of organometallic chemistry that deals with organic compounds featuring nickel-carbon bonds. They are used as a catalyst, as a building block in organic chemistry and in chemical vapor deposition. Organonickel compounds are also short-lived intermediates in organic reactions. The first organonickel compound was nickel tetracarbonyl Ni(CO)4, reported in 1890 and quickly applied in the Mond process for nickel purification. Organonickel complexes are prominent in numerous industrial processes including carbonylations, hydrocyanation, and the Shell higher olefin process.

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Organobismuth chemistry is the chemistry of organometallic compounds containing a carbon to bismuth chemical bond. Applications are few. The main bismuth oxidation states are Bi(III) and Bi(V) as in all higher group 15 elements. The energy of a bond to carbon in this group decreases in the order P > As > Sb > Bi. The first reported use of bismuth in organic chemistry was in oxidation of alcohols by Frederick Challenger in 1934 (using Ph3Bi(OH)2). Knowledge about methylated species of bismuth in environmental and biological media is limited.

<span class="mw-page-title-main">Organoindium chemistry</span> Chemistry of compounds with a carbon to indium bond

Organoindium chemistry is the chemistry of compounds containing In-C bonds. The main application of organoindium chemistry is in the preparation of semiconducting components for microelectronic applications. The area is also of some interest in organic synthesis. Most organoindium compounds feature the In(III) oxidation state, akin to its lighter congeners Ga(III) and B(III).

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<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.

In organometallic chemistry, metal–halogen exchange is a fundamental reaction that converts a organic halide into an organometallic product. The reaction commonly involves the use of electropositive metals and organochlorides, bromides, and iodides. Particularly well-developed is the use of metal–halogen exchange for the preparation of organolithium compounds.

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. C. Elschenbroich, A. Salzer Organometallics : A Concise Introduction (2nd Ed) (1992) from Wiley-VCH: Weinheim. ISBN   3-527-28165-7
  2. Chemistry of aluminium, gallium, indium, and thallium Anthony John Downs (Ed.) ISBN   978-0-7514-0103-5, 1993
  3. W, Uhl and M. R. Halvagar; et al. (2009). "Reducing Ga-H and Ga-C Bonds in Close Proximity to Oxidizing Peroxo Groups: Conflicting Properties in Single Molecules". Chemistry: A European Journal. 15 (42): 11298–11306. doi:10.1002/chem.200900746. PMID   19780106.
  4. Amemiya Ryo, Yamaguchi Masahiko (2005). "GaCl3 in Organic Synthesis". Eur. J. Org. Chem. 2005 (24): 5145–5150. doi:10.1002/ejoc.200500512.
  5. Organic Syntheses, Coll. Vol. 6, p.709 (1988); Vol. 55, p.70 (1976). Link