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CHM 609: Transition Metal Organometallic Chemistry (4)

Prerequisites: CHM 102, CHM 301, CHM 302

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.

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.

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

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.

Metal-element multiple-bonded complexes: Oxo, sulfido, imido, hydroazido, nitrido- complexes: Synthesis, bonding, structure, spectroscopy, and reactivity.

Complexes with metal-metal multiple bonds: Synthesis, structure and bonding, spectroscopic and magnetic properties, and reactions.

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.

Modern applications of organometallic chemistry: (a) Small molecule activation and functionalization: mechanistic and practical view. (b) Organometallic materials.

Suggested Readings :

• Crabtree, R. H. The Organometallic Chemistry of the Transition Metals, 3rd Ed.; Wiley-Interscience: New York, 2001.
• Hartwig, J. F.  Organotransition Metal Chemistry From Bonding to Catalysis, 1st Ed.; University Science Books: Sausalito, CA, 2010.
• 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.
• Spessard, G.O.; Miessler, G.L. Organometallic Chemistry. Prentice Hall: Upper Saddle River, NJ, 1996.
• Huheey, J.E.; Keiter, E.A.; Keiter, R.L. Inorganic Chemistry: Principles of Structure and Reactivity, 4th Ed.; HarperCollins: New York, 1993.
• Jordan, R. B. Reaction Mechanisms of Inorganic and Organometallic Systems;2nd Ed.; Oxford University Press: Oxford, 1998.
• (a) Bochmann, M. Organometallics 1; Oxford University Press: New York, 1994. (b) Bochmann, M. Organometallics 2; Oxford University Press: New York, 1994.
• Elschenbroich, C.; Salzer, A. Organometallics: A Concise Introduction, 2nd Ed.; VCH: New York, 1992.
• Shriver, D. F.; Atkins, P. W. Inorganic Chemistry, 3rd Ed.; W. H. Freeman: New York, 1999.
• Attwood, J. D. Inorganic and Organometallic Reaction Mechanisms, 2nd Ed.; VCH Publishers Inc.: New York, 1997.
• Nugent, W. A.; Mayer, J. A. Metal-Ligand Multiple Bonds, 1st Ed.; Wiley-Interscience, 1987.
• Elschenbroich, C. Organometallics, 3rd, Completely Revised and Extended Edition;Wiley-VCH Verlag GbmH & Co. KGaA, Weinheim, Germany, 2006.
• Cotton, F. A.; Murillo, C. A.; Walton, R. A. Multiple Bonds between Metal Atoms, 3rd Ed.; Springer Science Inc. New York, 2005.
• Primary literature (journal articles).

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