1. 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 http://creativecommons.org/about/license/(www.ionicviper.org http://creativecommons.org/about/license/

2. 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 http://creativecommons.org/about/license/(www.ionicviper.org http://creativecommons.org/about/license/

3. 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 http://creativecommons.org/about/license/(www.ionicviper.org http://creativecommons.org/about/license/

4. 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 http://creativecommons.org/about/license/(www.ionicviper.org http://creativecommons.org/about/license/

5. Formation of Aluminum Compounds  Alkylation: 2 Al + 3 CH 3 Cl  (CH 3 ) 3 Al 2 Cl 3 + 3 Na  (CH 3 ) 6 Al 2 + 3 NaCl  Metathesis: AlCl 3 + 3 RLi  R 3 Al + 3 LiCl  Transmetalation: 2 Al + 3 HgR 2 → 2 AlR 3 + 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 http://creativecommons.org/about/license/(www.ionicviper.org http://creativecommons.org/about/license/

6. Formation of Aluminum Compounds Polymeric AluminumMonomeric 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 http://creativecommons.org/about/license/(www.ionicviper.org http://creativecommons.org/about/license/

7. 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 http://creativecommons.org/about/license/(www.ionicviper.org http://creativecommons.org/about/license/

8. Selective Substitution and Ring Opening

9. Lithium Aluminum Hydride  Industrial synthesis 1.) Na + Al + 2 H 2 → NaAlH 4 2.) NaAlH 4 + LiCl → LiAlH 4 + NaCl  Used in reduction of carbonyls

10. 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 http://creativecommons.org/about/license/(www.ionicviper.org http://creativecommons.org/about/license/

11. 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 http://creativecommons.org/about/license/(www.ionicviper.org http://creativecommons.org/about/license/

12. 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/(www.ionicviper.org http://creativecommons.org/about/license/