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Chemistry 524: Organometallic Chemistry

Course Level: 
Graduate Level
Academic Year: 
2014/2015

MWF 11 am, D215

Recommended Textbook: Elschenbroich: Organometallics 3rd edition

The course will be a survey of bonding and reactivity in organometallic compounds with a heavy emphasis on the role of these compounds in catalysis.

Part I: Main Group Elements

A. Introduction and review 
1. General survey (i.e. introduction, nomenclature)
2. Types of compounds (ionic vs. covalent), types of ligands 
3. Bond energies and stabilities
4. Methods of formation of metal-carbon bonds of the main group elements

B. The Alkali Metals 
1. Organolithium compounds, MO description of electron-deficient bonding 
2. Li NMR spectroscopy
3. Sodium and the heavier alkalis, some reactivity, periodic trends

C. The Group 2 and 12 elements 
Group trends, synthesis, structure of coordination complexes,

D. The Group 13 elements 
1. Boron compounds: Synthesis, bonding, structure of
2. Aluminum compounds: Synthesis, bonding, structure of
3. Group trends: Ga, In, Tl (lower valence state)

E. The Group 14 elements 
1. Silicon
2. Heavier grp 14

F. The Group 15 elements 
Group trends, different possible oxidation states, phosphorus compounds

Part II: Transition Elements

A. Introduction 
1. MO description of bonding in octahedral compounds
2. MO basis for sigma vs. pi bonding
3. 18-electron rule and its applicability, electron counting
4. Group trends and IR spectroscopy
5. Isoelectronic and isolobal analogies

B. Organometallic Reactions
1. Ligand substitution
2. Insertion and elimination
3. Nucleophilic/electrophilic reactions
4. Oxidative addition/reductive elimination
5. Case study: Stille coupling, Heck reaction

C. s-Donor Ligands
1. Metal alkyls, aryls preparation, reactivity, 
2. Insertion/Elimination rxns case study: Ziegler Natta polymerization
3. Transition metal hydrides

D. s-Donor / p-Acceptor Ligands
1. Carbonyls
2. Phosphine ligands: electronics and sterics
3. Trans effect/ trans influence
4. Substitution reactions: mechanisms(D, A, I), kinetics
5. Complexes of RNC, N2, NO, and carbenes (bonding, reactivity as covered in class

E. p-Donor Ligands
1. Alkene, alkyne, allyl, butadiene ligands (MO description and bonding)
2. MO description of bonding in Cp and arene complexes
3. Bent metallocenes covered in Z/N section

F. Metal-Carbon Multiple Bonds
1. Fischer vs. Schrock Carbenes: properties, bonding description, reactivity
2. Singlet vs. triplet carbenes (cf maingroup analogues)
3. Synthesis of TM carbenes 
4. Metathesis: mechanism, ROMP