Organoaluminum
This presentation was created as part of the requirements for Chemistry 402 “Advanced
Inorganic Chemistry" at Elizabethtown College during the fall semester 2010. The authors of
this presentation are John Tellis and Zachary Kulp. (Elizabethtown College).
Created by John Tellis and Zachary Kulp, Elizabethtown College and posted on VIPEr (www.ionicviper.org) on January 5, 2011, Copyright John Tellis and Zachary
Kulp, 2011. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit
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Outline
Background
Synthesis
Ziegler-Natta Chemistry
Organic Reduction
Catalysis
o Aldol
o Guanidine synthesis
Created by John Tellis and Zachary Kulp, Elizabethtown College and posted on VIPEr (www.ionicviper.org) on January 5, 2011, Copyright John Tellis and Zachary
Kulp, 2011. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit
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Background
 Name proposed by Humphry Davy
o US: Aluminum
o Other: Aluminium
 Forms many dimeric and trimeric structures
 Applications
o Used to make many different alloys
• Metals include Cu, Mn, Mg, Si, Zn…
o Used in Drāno to unclog drains
o Protect cigarettes and hard candy from moisture
o Siding, furniture, and awnings
Created by John Tellis and Zachary Kulp, Elizabethtown College and posted on VIPEr (www.ionicviper.org) on January 5, 2011, Copyright John Tellis and Zachary
Kulp, 2011. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit
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Pure vs. Impure
Structurally weak
Corrosion-resistant
Readily reacts with water
Oxidizes easier than iron
Durable
Created by John Tellis and Zachary Kulp, Elizabethtown College and posted on VIPEr (www.ionicviper.org) on January 5, 2011, Copyright John Tellis and Zachary
Kulp, 2011. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit
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Formation of Aluminum Compounds
Alkylation:
2 Al + 3 CH3Cl  (CH3)3Al2Cl3 + 3 Na  (CH3)6Al2 + 3 NaCl
Metathesis:
AlCl3 + 3 RLi  R3Al + 3 LiCl
Transmetalation:
2 Al + 3 HgR2 → 2 AlR3 + 3 Hg
Created by John Tellis and Zachary Kulp, Elizabethtown College and posted on VIPEr (www.ionicviper.org) on January 5, 2011, Copyright John Tellis and Zachary
Kulp, 2011. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit
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Formation of Aluminum Compounds
Polymeric Aluminum
Monomeric Aluminum
Created by John Tellis and Zachary Kulp, Elizabethtown College and posted on VIPEr (www.ionicviper.org) on January 5, 2011, Copyright John Tellis and Zachary
Kulp, 2011. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit
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Ziegler-Natta Reaction
 MAO = methylaluminoxane
 Used as chloride abstractor in Ziegler-Natta reaction
Created by John Tellis and Zachary Kulp, Elizabethtown College and posted on VIPEr (www.ionicviper.org) on January 5, 2011, Copyright John Tellis and Zachary
Kulp, 2011. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit
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Selective Substitution and Ring Opening
Lithium Aluminum Hydride
Industrial synthesis
1.) Na + Al + 2 H2 → NaAlH4
2.) NaAlH4 + LiCl → LiAlH4 + NaCl
Used in reduction of carbonyls
Aldol Catalysis
Important reaction
Al acts as a Lewis Acid
Created by John Tellis and Zachary Kulp, Elizabethtown College and posted on VIPEr (www.ionicviper.org) on January 5, 2011, Copyright John Tellis and Zachary
Kulp, 2011. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit
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Amidoaluminum Catalyst
Used for synthesis of guanidines
Guanidine:
Created by John Tellis and Zachary Kulp, Elizabethtown College and posted on VIPEr (www.ionicviper.org) on January 5, 2011, Copyright John Tellis and Zachary
Kulp, 2011. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit
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References
 Larsen, S. C. Nanocrystalline Zeolites and Zeolite Structures: Synthesis,
Characterization, and Applications. J. Phys. Chem. 2007, 111, 18464-18474.
 Roesky, H. W. The Renaissance of Aluminum Chemistry. Inorg. Chem. 2004, 43,
7284-7293.
 Rodgers, G.E., Introduction to Coordination, Solid State, and Descriptive Inorganic
Chemistry. 1994, New York, NY: WBC/McGraw-Hill.
 Eisch, J. J. Reductive Deoxygenation of Ketones and Secondary Alcohols by
Organoaluminum Lewis Acids. J. Org. Chem. 1992, 57, 2143-2147.
 Duxbury, J. P.; Warne, J. N. D.; Mushtaq, R.; Ward, C.; Thornton-Pett, M.; Jiang, M.;
Greatrex, R.; Kee, T. P. Phospho-Aldol Catalysis via Chiral Schiff Base Complexes
of Aluminum. Organometallics 2000, 19, 4445-4457.
 Reddy, S. S. Methylaluminoxane: synthesis, characterization and catalysis of
ethylene polymerization. Polymer Bulletins 1996, 36, 165-171.
 Rowley, C. N. Amidolithium and Amidoaluminum Catalyzed Synthesis of
Substituted Guanidines: An Interplay of DFT Modeling and Experiment. Inorg.
Chem. 2008, 47, 9660-9668.
 Sasaki, M. Refioselective Alkul and Alkynyl Substitution Reactions of Epoxy
Alcohols by the Use of Organoaluminum Ate Complexes: Regiochemmical Reversal
of Nucleophilic Substitution Reactions. Organic Letters. 2001, 3, 1765-1767.
Created by John Tellis and Zachary Kulp, Elizabethtown College and posted on VIPEr (www.ionicviper.org) on January 5, 2011, Copyright John Tellis and Zachary
Kulp, 2011. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit
http://creativecommons.org/about/license/