HOME   |    TIGP  |    ACADEMIA SINICA       

 

Organometallic Chemistry

Credits: 3
Class hour: Monday 14:10-17:00
Place: P101 Meeting Room, 1F, Institute of Physics

Lecturers:

Dr. Ong, Tiow-Gan ¤ý´Â¿Î
Organometallics00@yahoo.ca

Objectives:

The fundamental transition-metal and organic chemistry merge to produce organometallic chemistry, a major area in its own right. This course aims at providing students with an appreciation of the following:

  • A knowledge of ligand-to-metal bonding and related synthetic, and spectroscopic aspects.
  • An understanding of the fundamental types of organometallic reaction, such as insertion, oxidative addition, reductive elimination, oxidative coupling, nucleophilic addition and electrophilic addition and how these key reactions operate in various important catalytic and non-catalytic processes.
  • The basic knowledge, skills and experience useful to those students progressing into the chemical industry or into research in either inorganic co-ordination chemistry, organometallic chemistry, or organic synthesis. The course will also be useful to those students requiring a current awareness of this major branch of chemistry.
  • An ability to read and appreciate the current literature in this area

Proposed Course Content:

The following outline is intended as a rough guide to the course. Subject to change!

A. Basic bonding concepts and M.O. theory.

¡E review of basic crystal field, ligand field, and M.O. theory
¡E ligand bonding and metal-ligand interactions
¡E £k-donors: alkoxides and amides
¡E £k-acceptors: CO and ethylene
¡E alkynes and cyclic systems: both £k-donors and acceptors
¡E allylic and cyclopentadienyl ligands

B. Organometallic concepts, terminology and nomenclature.

¡E electron counting and the 18 electron (EAN) rule
¡E neutral vs. charged counting schemes
¡E formal oxidation states
¡E relationship to M.O. theory
¡E exceptions to the 18 e - rule: stable d 8 16 e - complexes
¡E organometallic nomenclature

C. Structure and Bonding of Organometallic Complexes

¡E Transition Metal Alkyls and Aryls
¡E Metal Hydride Complexes and Other Related s-Bonded Ligands
¡E Metal Complexes of CO and Phosphine
¡E p-Bound Ligands such as Alkene and Alkyne complexes

D. NMR spectroscopy and fluxional processes.

¡E chemical shift norms
¡E heteronuclear NMR
¡E characterization: case studies
¡E fluxional processes: coalescence temperature and energy barriers
¡E examples of fluxional processes: hapticity changes and rotational barriers

E. Organometallic Reactions I: Reactions at the metal.

¡E ligand substitution
¡E oxidative-addition
¡E reductive-elimination

F. Organometallic Reactions II: Reactions involving the ligands.

¡E insertion and deinsertion of unsaturated substrates
¡E nucleophilic addition
¡E electrophilic reactions

G. Industrial homogeneous catalysis.

¡E basic principles
¡E hydroformylation
¡E hydrogenation/isomerization of alkenes
¡E Monsanto process
¡E Wacker process
¡E Ziegler-Natta polymerizations

H. Alkylidenes (carbenes) and alkylidynes (carbynes).

¡E bonding and formation
¡E nucleophilic vs. electrophilic alkylidenes
¡E alkene metathesis

I. Organometallics in organic synthesis.

¡E organometallics as protecting/activating groups
¡E Pd catalyzed coupling reactions (Heck, Stille, Suzuki, etc.)
¡E hydrozirconation
¡E metal-based cyclization reactions

Assigned text:

Organometallic Chemistry of the Transition Metals, Robert Crabtree, Wiley, Robert H. Crabtree, Fifth Edition.

Marking Scheme:

Attendance/Literature report: 30 %
Assignments or Quizzes: 10 %
Mid-term Exam 30 %
Final Exam 30 %