Chemistry 417/517                       Prof. D. M. Heinekey

Organometallics                                                                            heinekey@chem.washington.edu

TTh 10:00-11:20                                                                         

Winter 2021                                                                                                                  

Teaching Assistant: Cecilia Johnson (mcjohn2@uw.edu)

Zoom Meeting:
https://washington.zoom.us/j/92976174084?pwd=dElNRWhuWXBOMkpPbE1LUmRtS1hJQT09

Meeting ID: 929 7617 4084
Passcode: hydride

General Information:

This course will concentrate on the organometallic chemistry of the transition elements.  The first week will cover some main group chemistry.  It will be assumed that all students enrolled have completed formal courses in organic and inorganic chemistry at the undergraduate level.  If you do not meet these requirements, please consult me as soon as possible.

Required Textbook: Spessard and Miessler, Organometallic Chemistry 3^rd ed. (Wiley, 2015)

(Chem 517 students may substitute Hartwig’s Organotransition Metal Chemistry: From Bonding to Catalysis) (Univ. Science Books, 2010) – this is a great “keeper” shelf book for graduate students providing significant background, detail and a lot of references.  Well-worth the price and highly recommended!

Other Useful Textbooks: To help in understanding a topic, rather than re-reading the same text multiple times, it is very helpful to read about the same topic in an alternate source.  Among others, you may find the following alternate texts useful.

Crabtree, The Organometallic Chemistry of the Transition Metals 6th ed. (Wiley, 2014)   

Eischenbroich, Organometallics (VCH, 2006) – also includes main-group organometallic chemistry

Atwood, Inorganic and Organometallic Reaction Mechanisms (Brooks/Cole, 1998)

Topics

1. Main Group chemistry
2. Introduction to Transition Metals/Bonding/Electron Counting
3. Carbonyls, Phosphines, Ligand Substitution
4. Alkyls and Hydrides
5. Characterization/Spectroscopy
6. Alkene, Diene complexes
7. Oxidative Addition/Reductive Elimination
8. Insertion/Elimination
9. Nucleophilic/Electrophilic Addition
10. Homogeneous Catalysis
11. Metal-Ligand Multiple Bonds
12. Polymerization/Metathesis
13. Biological Organometallic Chemistry

Web Resources: The following resources available on the internet have not undergone critical review but you may find them useful as supplemental materials to lectures and your textbook.

http://chem-faculty.lsu.edu/stanley/Chem4571-stanley.htm (lecture notes)

http://www.scs.illinois.edu/white/index.php?p=lectures (lecture notes)

http://web.uvic.ca/~mcindoe/423/423syllabus.html (list of useful organometallic textbooks some with links providing free limited previews)

http://www.ilpi.com/organomet/ (Organometallic HyperTextBook- has had limited updates)

Problem Sets:                      

Problems sets will be assigned and typically you will have a week to complete the work.  Unless directed otherwise for a particular homework assignment, you may work in groups on the assignments.  However, everyone must submit individual answer sets.  In addition, please include the names of the other individuals in your group.  This helps us to understand in general how students are grasping the course content.  On the day when problem sets are due, we will work the problems together.  You are free to revise your submissions.

Literature Assignment:     

There will be a writing assignment that will require you to make use of the current literature in transition metal organometallic chemistry. This assignment will be a larger project for Chem 517 students.

Exams:                                  

A midterm exam (Tuesday, Feb. 16th) and a comprehensive final exam (Monday, March 15th, 10.30-12.20 PM). There will be no makeup exams.

Tentative Grade Composition:          

                                                417:           Midterm Exam                        150 pt

                                                              Final Exam                               250 pt

                                                              Literature assignment             100 pt

                                                              Problem sets                  ca. 70-100pt

                                                517:           Midterm Exam                        150 pt

                                                              Final Exam                               250 pt

                                                              Literature assignment             150 pt

                                                              Problem sets                ca. 100-150pt

Literature Assignment -Due Thursday March 4 [Comm must be chosen by Thursday February 25]

           The Journal of the American Chemical Society (JACS) and Angewandte Chemie are considered the premier journals which cover all areas of Chemistry.  Articles and communications are selected on the basis of their significance and interest to a broad audience. All manuscripts are rigorously reviewed by experts in the field prior to publication. 

           You should choose a recent communication (last three years) published in JACS or Angewandte that reports on an organometallic complex(es).  The organometallic complex itself or its reactions should be the main focus of the publication.  Obtain the instructor's approval on your choice of article before proceeding to prepare your report.

Discuss the article in a 2-3 page report(double-spaced).  You should attempt to address the following:  

Condensation of the Research:

(1) A concise description of the research set forth in the communication-what the authors accomplished.  Please feel free to use pictures or schemes in your discussion.

(2) Include a list of the specific experimental findings and the conclusions drawn by the researchers.  A description of what techniques were employed in this work should also be presented. 

Commentary on the Research:

(1) Validity of Experimental Work and Conclusions.  Were the experiments well thought out? Were the conclusions fair? 

(2)  Significance.  Why is this work important? 

(3)  What related complexes or reactions might the researchers turn to study in future work?  Or what additional work should be accomplished to fully understand this system?

Relation to this course:

Attempt to relate the complexes or reactions in this paper to material that we have covered. Your paper should include some of the following:

(1) The electron count and formal oxidation state of the metal or metals involved in the complex. 

(2) comment on an isolobal relation.

(3) discuss CO stretching frequencies and their relation to the other ligands present

(4) discuss the NMR data including coupling to the metal and phosphorus atoms or other spin active atoms in the complex.

(5) Point out fundamental organometallic reaction steps in the paper and comment on any stereochemical issues.

(6) Discuss any kinetic observations presented in the paper.

(7) Point out a typical method of preparing a particular type of compound-e.g.. Grignard reagent + metal halide

In addition to your discussion, you must also submit a photocopy of the article.

NOTE:  To prevent duplication of communications, you must receive the instructor's approval.  The teaching assistant will maintain a list available on the web site. If the contribution you have chosen is already listed, you need to choose another.  Deadline for finalizing your choice is February 25.  

Additional Literature Assignment for 517 Students.  (Due March 11^th)

Some published papers in the literature are not correct.  Some of these errors are corrected in subsequent publications.  This can be found using the citation indexes aka Web of Science, see http://apps.webofknowledge.com

A separate list of publications will be made available. For each of the publications, use the citation index to find the correction.  Write a brief explanation of what went wrong and how it was corrected. (100-200 words).