Organoaluminium
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An organoaluminium compound is an organometallic compound with a carbon to aluminium bond.[1]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 | ||||
| Core organic chemistry | many uses in chemistry. |
| Academic research, but no widespread use | Bond unknown / not assessed. |
References
Acknowledgement and Attribution Regarding Sources of Content
Some of the initial content on this page may be incorporated in part from copyleft sources in the public domain including wikis such as Wikipedia and AskDrWiki. Drug information for patients came from the The National Library of Medicine. Infectious disease information may have come from the Centers for Disease Control (CDC). Differential Diagnoses are drawn from clinicians as well as an amalgamation of 3 sources: 1.The Disease Database; 2. Kahan, Scott, Smith, Ellen G. In A Page: Signs and Symptoms. Malden, Massachusetts: Blackwell Publishing, 2004:3; 3. Sailer, Christian, Wasner, Susanne. Differential Diagnosis Pocket. Hermosa Beach, CA: Borm Bruckmeir Publishing LLC, 2002:7 .
