Course Title: Transition Metal Organometallic Chemistry

Course No.: CHM 609

Course Contents:

1. Structure and bonding: Brief overview of transition metal orbitals, electron counting, formal oxidation state, 18-e rule and its exceptions, isoelectronic and isolobal analogies, common geometries for transition metal complexes (Crystal Field Theory, MO description), σ- and π-bonding, types of ligands and their properties, soft vs hard ligands.

2. Reactions of organometallic complexes: ligand substitution/exchange/dissociation processes and thermochemical considerations, catalyzed and assisted ligand substitution reactions, oxidative addition (definition, mechanism, thermodynamic consideration), oxidative addition of non-polar and polar electrophilic reagents, reductive elimination (bite angle effects, π-acid effects), transmetallation (definition, mechanism, utility), insertion/de-insertion, nucleophilic and electrophilic attack on coordinated ligands.

3. Complexes with classic Lewis base donors: Amines, phosphines and other related donors.

4. Complexes with metal‐carbon σ‐bonds:

(a) Metal carbonyl complexes: Synthesis, structure and bonding; IR spectroscopy; Reactions; Related complexes with cyanide, nitrosyl, and dinitrogen ligands. (b) Metal alkyl complexes: Synthesis, stability and structure; Reactions; Activation of C‐H bonds. (c) Alkylidene and alkylidyne complexes: Synthesis; structure and bonding; Reactivity; Olefin metathesis.

5. Metal complexes of π‐ligands:

(a) Alkene complexes: Synthesis; Bonding; Reactivity. (b) Alkyne complexes: Synthesis; Bonding; Reactivity. (c) Cyclopentadienyl complexes: Discovery of ‘sandwich’ complexes; Bonding; Properties of Cp complexes of 3d metals; Substituted metallocenes; Zigler‐Natta polymerization; Half-sandwich complexes. (d) Allyl and dienyl complexes: Synthesis; Structure and properties; Reactivity. (e) Arene complexes: Bis‐arene complexes; Arene half‐sandwich complexes; η2 to η4 coordinated arenes; Seven and eight‐membered ring ligands.

6. Classics of homogeneous catalysis: Hydrogenations, hydroformylations, olefin polymerization, metathesis, carbonylation.

7. Modern applications of organometallic chemistry:

(a) Small molecule activation and functionalization: mechanistic and practical view.

(b) Organometallic materials.

Selected Readings:

1. Crabtree, R. H. The Organometallic Chemistry of the Transition Metals, 3rd Ed.; Wiley-Interscience: New York, 2001.

2. Hartwig, J. F. Organotransition Metal Chemistry From Bonding to Catalysis, 1st Ed.; University Science Books: Sausalito, CA, 2010.

3. Collman, J.P.; Hegedus, L.S.; Norton, J.R.; Finke, R.G. Principles and Applications of Organotransition Metal Chemistry; University Science: Mill Valley, CA, 1987.

4. Spessard, G.O.; Miessler, G.L. Organometallic Chemistry. Prentice Hall: Upper Saddle River, NJ, 1996.

5. Huheey, J.E.; Keiter, E.A.; Keiter, R.L. Inorganic Chemistry: Principles of Structure and Reactivity, 4th Ed.; HarperCollins: New York, 1993.

6. Jordan, R. B. Reaction Mechanisms of Inorganic and Organometallic Systems; 2nd Ed.; Oxford University Press: Oxford, 1998.

7. (a) Bochmann, M. Organometallics 1; Oxford University Press: New York, 1994. (b) Bochmann, M. Organometallics 2; Oxford University Press: New York, 1994.

8. Elschenbroich, C.; Salzer, A. Organometallics: A Concise Introduction, 2nd Ed.; VCH: New York, 1992.

9. Shriver, D. F.; Atkins, P. W. Inorganic Chemistry, 3rd Ed.; W. H. Freeman: New York, 1999.

10. Attwood, J. D. Inorganic and Organometallic Reaction Mechanisms, 2nd Ed.; VCH Publishers Inc.: New York, 1997.

11. Primary literature (journal articles).