Instructor:  Dr. Holly D. Bendorf                                                              Phone:  x4365, 327-2888
Office:  209 HBC                                                                                      e-mail:  bendorf@lycoming.edu

Course Schedule:         Lecture:    MWF  11:30 - 12:20
                                      Lab: R  1:00 - 4:50

Office Hours:  By appointment or walk-in.

Course Description:  CHEM 450, Organometallic Chemistry, explores the chemistry of compounds containing metal-carbon bonds.  This course will cover the structure and bonding of organometallic compounds, their reactions and reaction mechanisms, spectroscopy, and their use in industrial processes and organic synthesis.

Text and Materials:

• "Organometallic Chemistry" by Gary Spessard and Gary Miessler, Prentice-Hall, 1997.
• Bound laboratory notebook (Freeman).
• Safety glasses or goggles.
• Lab breakage deposit of $10, refunded upon check-out.

Grading Criteria:
 

Quizzes and Assignments	150 points	20%
Exams	200 points	27%
Laboratory	150 points	20%
Research Paper and Presentation	100 points	13%
Final Exam	150 points	20%
	750 points	100%

 
Exams:  There will be two exams administered during the lab period on the following dates:
Thursday, February 18 and Thursday, April 1.  The final exam will be administered on the day and time assigned by the registrar.

Assignments:  A portion of your grade will be based on in-class and take-home assignments.  Be aware that in accordance with the College's policy on academic honesty, any work you turn in must be your own.  Any instances of plagiarism (including copying answers from a classmate) will be penalized severely.  All take-home assignments are due at the beginning of the class period.  Late homework will not be accepted.

Reading Assignments:  Readings from the text and chemical literature will be assigned on a regular basis.  You should complete these assignments in a timely manner as they will form the basis of our in-class discussions.  Please be aware that ten points of the quiz and assignment grade is based on participation in class discussions.

Research Paper and Presentation:   You will research and write a 10-page paper on an organometallic chemistry topic of your choice.  During the last week of the semester, you will give a 15-20 minute presentation on your topic to the class.  One lab meeting will be set aside for students to give practice talks with one or two other students and the instructor present.

  Timeline:    Topic due:  January 29
                    References and Outline due:  February 15
                    First Draft due:  March 12
                    Peer Review of first draft due:  March 17
                    Report due:  March 29
                    Practice Talks:  April 15
                    Presentations to Class:  April 21, 22, 23
 
Extra Credit:  Extra credit points (3) can be earned by attending departmental colloquia.  Any extra credit points earned will be used to nullify unexcused absences from class (see below) before they will be applied to one's grade.  Extra credit is limited to 20 points.
 
Attendance:  Regular attendance at lecture and laboratory sections is expected, and repeated, unexcused absences will be penalized (3 points per absence).  Attendance at quizzes, exams and laboratory meetings is mandatory.  Make-ups are not  permitted unless the absence has prior approval by me (usually a case of medical or family emergency which can be documented).  A single, cumulative make-up exam will be administered at the end of the semester.  Quizzes cannot be made-up.  In case of an emergency, I can also be reached at my home: 327-2888.

Course Outline:   See attached pages.

Laboratory:   The lab portion of the course is composed of five experiments and one exercise to develop techniques for handling air sensitive chemicals.  Lab reports will follow the format of a JACS or JOC article and will include the following sections:  Introduction and background, results and discussion, experimental, and references.   Additional information on writing reports will be given in class.

Lab Schedule:

Jan. 14       Check-in

Jan. 21       Lab 1:  Synthesis of Metal Nitrosyl Complexes

Jan. 28       Characterize Products from Nitrosyl Lab
                  Handling Air-Sensitive Materials:  Lecture, Demo and Hands-on Practice

Feb. 4        Lab 2:  Synthesis of Ferrocene
                  ** Report on Lab 1 due.

Feb. 11      Characterize Ferrocene
                  Lab 3:  Synthesis of Wilkinson's Catalyst

Feb. 18      Exam 1

Feb. 25      Decarbonylation of an Aldehyde using Wilkinson's Catalyst
                  ** Report on Lab 2 due.

Mar. 11     Lab 4:  Lab Project (TBA)

Mar. 18     Lab 4

Mar. 25     Lab 4
                  ** Report on Lab 3 due.
 
Apr. 1        Exam 2

Apr. 8         Lab 5:  Ring-Opening Metathesis Polymerization
                  ** Report on Lab 4 due.

Apr. 15       Practice Talks

Apr. 22       Check-out
                   ** Report on Lab 5 due.

Lab Safety:  Unsafe behavior in the lab will not be tolerated and violations will be penalized.  Repeated violations during a class may result in a zero for that lab.  Keep in mind that lab safety includes laboratory hygiene.  In the event that common areas are left dirty, (rotovaps, balances, melting point apparati, reagent hood) points may be deducted from the entire class.  If you have any questions regarding lab safety, please do not hesitate to ask.

Part I: Structure and Bonding

A.  Introduction to Organometallic Chemistry
     1.  Definition and examples
     2.  History
     3.  Modern Applications

B.  Structure and Bonding in Organometallic Complexes:  The Basics
     1.  EAN Rule (18 electron rule)
     2.  Coordination number and geometry
     3.  Hard-Soft/Acid-Base Theory
     4.  Crystal Field Theory
     5.  Molecular Orbital Theory

C.  Metal-Ligand Bonding and Back-bonding
     1.  Carbonyls
     2.  Carbenes
     3.  Phosphines
     4.  Alkenes
     5.  Alkynes
     6.  Polyenes
     7.  Hydrides and Dihydogen complexes
 
D.  Spectroscopy of Organometallic Complexes
     1.  Infrared
     2.  NMR
     3.  Fluxionality and Dynamic Complexes
 

Part II. Reactions and Reaction Mechanisms

A.  Survey of the Major Reaction Types
     1.  Coordination Changes
     2.  Ligand Substitution
     3.  Oxidative Addition
     4.  Reductive Elimination
     5.  Insertion and  Elimination
     6.  Oxidative Cyclization/Coupling
     7.  Nucleophilic Addition
     8.  Electrophilic Addition

B.  Ligand Substitution
     1.  Associative Mechanism
          a.  trans effect/influence
          b.  synthesis
     2.  Dissociative Mechanism
     3.  Radical Mechanism

C.  Oxidative Addition
     1.  Requirements for the reaction
     2.  Polar Mechanism
     3.  Non-Polar Mechanism
            Oxidative Addition of Alkanes:  C-H activation
     4.  Radical Mechanism

D.  Reductive Elimination
     1.  Requirements for the reaction
     2.  Mechanism
     3.  Stereochemistry

E.  Insertion and Elimination
     1.  1,1-Insertions:  CO Insertion
          a.  Mechanism
          b.  Stereochemistry
          c.  Migratory aptitudes
          d.  Applications:  Monsanto Acetic Acid Process
     2.  Elimination:  Decarbonylation
     3.  1,2-Insertions:  Alkene and Alkyne Insertion
          a.  Mechanism
          b.  Stereochemistry
          c.  Applications:  Hydrogenation and chiral catalysis (L-Dopa synthesis),        Hydroformylation
     4.  b-Hydride Elimination
          a.  requirements
          b.  Heck Reaction
     5.  Polymerization

F.  Additions to Ligands
     1.  Nucleophilic Addition
          a.  Green's Rules
          b.  Applications:  Wacker Process, Pd p-allyl chemistry, b-lactam prep'n
          c.  Nucleophilic Abstraction
     2.  Electrophilic Addition and Abstraction

G.  Oxidative Coupling and Cyclizations
     Applications to organic synthesis