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Organoaluminium



An organoaluminium compound is an organometallic compound with a carbon to aluminium bond.[1]

Additional recommended knowledge

Contents

History

Organoaluminium compounds, little known until the 1950s, have become widely accepted and increasingly important in the field of industry and in the laboratory, particularly after the work of Karl Ziegler and colleagues, who discovered the direct synthesis of trialkylaluminiums and their application to olefin polymerization. A comprehensive review of organoaluminium chemistry appeared in 1972, covering a variety of literature up to late 1971. Other important review articles have been published since then.

Special properties

Generally Al prefers to have >3 coordination due to electron deficiency unless R groups are very bulky, e.g. Al(Mes)3 (Mes = 2,4,6-Me3C6H2 or mesityl). The chemistry of organoaluminium compounds can be understood in terms of the dynamic nature of the C−Al bond and the high Lewis acidity of the monomeric species.

A good example of the dynamic nature of the C−Al bond is the dimer, Al2Me6.

Al−C−Al bridging persists in non-donor solvents with fast Al-Me exchange which can be confirmed by proton NMR. At −25°C the 1H NMR of Me6Al2 comprises two signals in 1:2 ratio, as expected from the solid state structure. At 20°C, only one signal is observed because exchange of terminal and bridging methyls is too fast to be resolved by NMR. The high Lewis acidity of the monomeric species is directly related to the pronounced tendency of the aluminium atom to build up an octet of electrons.

Laboratory Preparation of organoaluminium

R3Al can be prepared by either metathesis or transmetalation in the laboratory.

  • Metathesis with RLi or RMgX
AlCl3 + 3 BuLi → Bu3Al + 3 LiCl
  • Transmetalation
2 Al + 3 HgPh2 → 2 AlPh3 + 3 Hg
  • Industrially, simple aluminium alkyls (Me, Et) can be prepared by a direct process.
4 Al + 6MeCl → 2 Me3Al2Cl3 → Me4Al2Cl2 + Me2Al2Cl4 → Me4Al2Cl (l) + 2 Na[MeAlCl3] (s) → Me3Al + Al + 6 NaCl

Reactions of organoaluminium compounds

  • Organoaluminium compounds are hard acids and readily form adducts with bases such as pyridine, THF and amines.
  • Reaction with protic reagents:
AlR3 + ROH → (R2Al−OR)n + RH
  • Hydroalumination of C=C double bonds
  • Industrially, organoaluminium compounds can be used as catalysts for alkene polymerisation to polyolefins.

See also

CH He
CLi CBe CB CC CN CO CF Ne
CNa CMg CAl CSi CP CS CCl Ar
CK CCa CSc CTi CV CCr CMn CFe CCo CNi CCu CZn CGa CGe CAs CSe CBr Kr
CRb CSr CY CZr CNb CMo CTc CRu CRh CPd CAg CCd CIn CSn CSb CTe CI Xe
CCs CBa CHf CTa CW CRe COs CIr CPt CAu CHg CTl CPb CBi CPo CAt Rn
Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq Uup Uuh Uus Uuo
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa CU Np Pu Am Cm Bk Cf Es Fm Md No Lr


Chemical bonds to carbon
Core organic chemistry many uses in chemistry.
Academic research, but no widespread use Bond unknown / not assessed.

References

  1. ^ Atkins inorganic chemistry, organometallic compounds.
 
This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Organoaluminium". A list of authors is available in Wikipedia.
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