CHEM.4680 Course Outline

Textbook(s):
Robert H. Crabtree, The Organometallic Chemistry of the Transition Metals, 4th Ed. (Wiley, 2005)
Recommended Supplements:
Christoph Elschenbroich, Albrecht Salzer, Organometallics, 2nd Ed. (VCH, 1992), p 15-56 (groups 1 and 2) and 75-146 (Al-Tl, Si-Pb)

General outline: The course covers the organometallic chemistry of main-group and transition metals, and their relevance to organic synthesis and homogeneous catalysis. Topics include:

  1. Electron counting. The 8/18-electron "rule" and its exceptions. Relation to reactivity and stability. Multi-center (2e-3c and 2e-4c) bonding. Formal oxidation states.
  2. Main-group metal chemistry: electropositive elements. Synthesis, use as intermediates in organic synthesis. Reactivity as nucleophile, base and reductant.
  3. Main-group metal chemistry: less electropositive elements (mainly silicon). Synthesis and applications.
  4. NMR of organometallic compounds. Symmetry and fluxionality.
  5. Transition-metal organometallic chemistry: metal-ligand bonding, standard synthesis and decomposition routes.
  6. Ligand substitution and activation.
  7. Insertion and elimination reactions, including olefin polymerization and s-bond metathesis.
  8. Oxidative addition and reductive elimination.
  9. Olefin metathesis.

Optional special topics:

  1. Hot topics and hypes in organometallic chemistry.
  2. Separation of steric and electronic effects (Tolman c, q; QALE).
  3. Chiral catalysis.
  4. C-H activation.
  5. Modelling of organometallic reactions.

Ca 3/4 into the course, students are expected to present a recent paper (to be selected during the course).

At the end of the course, students should be able to draw "reasonable" mechanisms for most reactions of homogeneous catalysis (and provide alternatives), should be able to understand the effects of ligand variation and should have an overview of organometallic reactions commonly used in organic synthesis.

There is no laboratory work in this course.

Final grading:

Assignments 10%
Presentation 20%
Mid-term 20%
Final 50%

The mid-term exam will be a standard written exam. No notes or other relevant material can be brought to this exam.

The final exam is also a written exam, but is open-book. Any written material can be brought, including the Crabtree book, course notes, and any other written material you might find useful. However, electronic aids (phones, computer, organizers) are not permitted. A simple calculator (not containing any text material) is allowed, but is unlikely to be useful. Please note that open-book does not mean this exam is easier than the mid-term!

Prerequisite:

Either CHEM 3380 (Inorganic Chemistry)

Or CHEM 3390 (Structural Transformations in Organic Chemistry)