Energetics and catalysis in organic reactions. Pericyclic Reactions; Substituent Effects; Linear Free Energy Relationships. Prerequisite: Chemistry 313 or 330.
A.Perturbation Molecular Orbital Theory
HOMO-LUMO Interactions, Frontier Molecular Orbitals, Aromaticity, Odd and Even Alternant Hydrocarbons, Pericyclic Reactions (Cycloadditions, Electrocyclic Reactions, Sigmatropic Rearrangements), The Woodward-Hoffman Rules.
B.Thermodynamic and Kinetic Analysis of Organic Reactions
Free Energy Changes, The Arrhenius Equation, Transition State Theory, The Eyring Equation, Diffusion Controlled Reactions, The Mechanistic Significance of D H‡ and D S‡, Kinetic versus Thermodynamic Control of Organic Reactions, The Hammond Postulate, The Curtin-Hammett Principle; Kinetic Isotope Effects, The Reactivity-Selectivity Principle, Substituent Effects, the Hammett Equation, Linear Free Energy Relationships.
Absorption of Light by Organic Molecules, Jablonsky Diagrams, Morse Potential Energy Curves, n,p * versus p ,p * Excited States, Singlets and Triplets, Quantum Yields, Triplet-Triplet Energy Transfer, Stern-Volmer Kinetics, Examples of Common Photochemical Reactions (Norrish Type I and II Reactions, [2+2] Photocycloadditions, Oxetane Formation, The Di-p -Methane Rearrangement, Enone Photorearrangements, cis,trans-Photoisomerization of Alkenes, Singlet Oxygen Reactions).
J.A. Hirsch, "Concepts in Theoretical Organic Chemistry, Allyn and Bacon, 1974.
I. Fleming, "Frontier Orbitals and Organic Chemical Reactions," Wiley, 1976.
T.H. Lowry and K.S. Richardson, "Mechanism and Theory in Organic Chemistry, 3rd Ed., Harper and Row, 1987.
F.A. Carey and R.J. Sundberg, "Advanced Organic Chemistry," 3rd Ed., Plenum, 1990, Part A.
J. March, "Advanced Organic Chemistry - Reactions, Mechanisms and Structure, 4th Ed., Wiley, 1992.
A. Pross, "Theoretical and Physical Principles of Organic Reactivity," Wiley, 1995.
B. Miller, "Advanced Organic Chemistry," Prentice-Hall, 1998.
F.A. Carroll, "Perspectives on Structure and Mechanisms in Organic Chemistry," Brooks-Cole, 1998.